Polycyclic compounds

Abstract

The present invention relates to compounds having polycyclic structural units and to electronic devices, in particular organic electroluminescent devices, containing said compounds.

Claims

1. A compound of formulae (Ia) or (IIa): ##STR00239## wherein X is the same or different in each instance and is CR or N; Y is or phenyl; R is the same or different in each instance and is H, D, F, Cl, I, N(R.sup.1).sub.2, CN, NO.sub.2, OH, COOH, C(O)N(R.sup.1).sub.2, Si(R.sup.1).sub.3, B(OR.sup.1).sub.2, C(O)R.sup.1, P(O)(R.sup.1).sub.2, S(O)R.sup.1, S(O).sub.2R.sup.1, OSO.sub.2R.sup.1, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, each of which is optionally substituted by one or more R.sup.1 radicals, wherein one or more hydrogen atoms are optionally replaced by D or F, an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms and is optionally substituted in by one or more R.sup.1 radicals, an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.1 radicals, an aralkyl or heteroaralkyl group which has 5 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.1 radicals, or a diarylamino group, diheteroarylamino group, or arylheteroarylamino group which has 10 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.1 radicals; and wherein two adjacent R radicals together optionally define a mono- or polycyclic, aliphatic, aromatic, or heteroaromatic ring system; R.sup.1 is the same or different in each instance and is H, D, F, Cl, Br, I, N(R.sup.2).sub.2, CN NO.sub.2, Si(R.sup.2).sub.3, B(OR.sup.2).sub.2, C(O)R.sup.2, P(O)(R.sup.2).sub.2, S(O)R.sup.2, S(O).sub.2R.sup.2, OSO.sub.2R.sup.2, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, each of which is optionally substituted by one or more R.sup.2 radicals, wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by R.sup.2CCR.sup.2, CC, Si(R.sup.2).sub.2, CO, NR.sup.2, O, S, or CONR.sup.2 and wherein one or more hydrogen atoms are optionally replaced by D, F, Cl, Br, I, CN, or NO.sub.2, an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms and is optionally substituted by one or more R.sup.2 radicals, an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.2 radicals, an aralkyl or heteroaralkyl group which has 5 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.2 radicals, or a diarylamino group, diheteroarylamino group, or arylheteroarylamino group which has 10 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.2 radicals; and wherein two or more adjacent R.sup.1 radicals together, or R.sup.1 together with R, optionally define a mono- or polycyclic, aliphatic, aromatic, or heteroaromatic ring system; R.sup.2 is the same or different in each instance and is H, D, F, or an aliphatic, aromatic, and/or heteroaromatic hydrocarbyl radical having 1 to 20 carbon atoms, wherein one or more hydrogen atoms are optionally replaced by F; and wherein two or more R.sup.2 radicals together optionally define a mono- or polycyclic aliphatic ring system.

2. The compound of claim 1, wherein the compound comprises a structure of formulae (Ia1), (Ia2), (IIa1), or (IIa2): ##STR00240##

3. The compound of claim 1, wherein the compound comprises a structure of formulae (Ia3) or (Ia4): ##STR00241##

4. The compound of claim 1, wherein the compound comprises structures of formula CyE-(CyF).sub.n, wherein: n is 2 or 3 CyE is a structural element selected from the group consisting of formulae (CyE-1) through (CyE-27): ##STR00242## ##STR00243## ##STR00244## ##STR00245## CyF is at least one structural element selected from the group consisting of formulae (CyF-3) and (CyF-4): ##STR00246## wherein U is selected from the group consisting of O, S, C(R).sub.2, N(R), B(R), Si(R).sub.2, CO, SO, SO.sub.2, P(R) and P(O)R; and the dotted line in formulae (CyF-3) and (CyF-4) denotes the bond to the CyE group, and CyF group bonds to CyE in each case at the position denoted by #.

5. The compound of claim 1, wherein the compounds have structures of formula CyG(CyH).sub.n, wherein CyG and CyH together in each case defined a ring and: n is 2 or 3 CyG is a structural element selected from the group consisting of formulae (CyG-1) through (CyG-17): ##STR00247## ##STR00248## and CyH is at least one structural element selected from the group consisting of formulae (CyH-1) (CyH-2) ##STR00249## wherein U is selected from the group consisting of O, S, C(R).sub.2, N(R), B(R), Si(R).sub.2, CO, SO, SO.sub.2, P(R), and P(O)R; and the dotted line in formulae CyH-1 and CyH-2 denotes the bond to CyG, and CyH bonds to CyG in each case at the positions denoted by o so as to define a ring.

6. The compound of claim 1, wherein the compound is in the form of an enantiomer mixture.

7. The compound of claim 1, wherein the definitions for X are selected such that the ratio of CR to N is greater than or equal to 3.

8. The compound of claim 1, wherein the compound has a glass transition temperature of at least 110 C.

9. The compound of claim 1, wherein the compound has a molecular weight of not more than 5000 g/mol.

10. A composition comprising at least one compound of claim 1 and at least one further organic functional material selected from the group consisting of fluorescent emitters, phosphorescent emitters, host materials, matrix materials, electron transport materials, electron injection materials, hole conductor materials, hole injection materials, electron blocker materials, and hole blocker materials.

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

12. An electronic device comprising at least one compound of claim 1.

13. The electronic device of claim 12, wherein the electronic device is selected from the group consisting of organic electroluminescent devices.

14. The compound of claim 6, wherein the compound is in the form of a diastereomer mixture.

15. The electronic device of claim 13, wherein the electronic device is an organic electroluminescent device selected from the group consisting of organic laser diodes, organic light-emitting transistors, organic light-emitting diodes, organic light-emitting electrochemical cells, organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic solar cells, organic optical detectors, organic photoreceptors, and organic field quench devices.

16. The compound of claim 1, wherein the compound is selected from the group consisting of compounds 1-13, 14a, 14b, 16, 17, 20, 26-36, 38-42, 44-46, 48-84, A32, A39, A42, A44, B3, D4, A57, A58, and A59: ##STR00250## ##STR00251## ##STR00252## ##STR00253## ##STR00254## ##STR00255## ##STR00256## ##STR00257## ##STR00258## ##STR00259## ##STR00260## ##STR00261## ##STR00262## ##STR00263## ##STR00264##

Description

EXAMPLES

(1) The syntheses which follow, unless stated otherwise, are conducted under a protective gas atmosphere in dried solvents. The metal complexes are additionally handled with exclusion of light or under yellow light. The solvents and reagents can be purchased, for example, from Sigma-ALDRICH or ABCR. The respective figures in square brackets or the numbers quoted for individual compounds relate to the CAS numbers of the compounds known from the literature.

(2) General Preparation Method:

(3) Reaction of Monoaldehyde with Monoamine and Monoolefin

(4) ##STR00054##

(5) To a well-stirred mixture of 500 mmol of the arylamine, 550 mmol of the arylaldehyde, 1 mol of the activated olefin and 1300 mL of dichloromethane are added 100 mmol of the Lewis acid, and then the mixture is heated under reflux for 40 h. After cooling, the reaction mixture is washed twice with 400 mL each time of water, the organic phase is dried over magnesium sulfate and then the dichloromethane is removed under reduced pressure. The residue is taken up in 1000 mL of o-dichlorobenzene, 5 mol of manganese dioxide are added and the mixture is heated under reflux on a water separator for 16 h. After cooling, 1000 mL of ethyl acetate are added, the manganese dioxide is filtered off with suction through a Celite layer, the manganese dioxide is washed with 1000 mL of ethyl acetate and the combined filtrates are freed of the solvents under reduced pressure. The residue is recrystallized and finally freed of low boilers and nonvolatile secondary components by fractional sublimation (p about 10.sup.4-10.sup.6 mbar, T about 150-400 C.). Compounds having a molar mass greater than about 1200 g/mol are preferably freed of solvent residues by heat treatment under high vacuum.

(6) If polyfunctional starting materials are used, the stoichiometry is adjusted correspondingly.

Example A1

7,8,9,10-Tetrahydro-7,10-methano-6-phenylphenanthridine

(7) ##STR00055##

(8) To a well-stirred mixture of 46.6 g (500 mmol) of aniline [62-63-3], 58.4 g (550 mmol) of benzaldehyde [100-52-7], 94.2 g (1 mol) of norbornene [498-66-8] and 1300 mL of dichloromethane are added dropwise 14.2 g (100 mmol) of boron trifluoride etherate [60-29-7], and then the mixture is heated under reflux for 40 h. After cooling, the reaction mixture is washed twice with 400 mL each time of water, the organic phase is dried over magnesium sulfate and then the dichloromethane is removed under reduced pressure. The residue is taken up in 1000 mL of o-dichlorobenzene, 435 g (5 mol) of manganese dioxide are added and the mixture is heated under reflux on a water separator for 16 h. After cooling, 1000 mL of ethyl acetate are added, the manganese dioxide is filtered off with suction through a Celite layer, the manganese dioxide is washed with 1000 mL of ethyl acetate and the combined filtrates are freed of the solvents under reduced pressure. The residue is recrystallized twice from cyclohexane and finally freed of low boilers and nonvolatile secondary components by fractional sublimation (p about 10.sup.4-10.sup.5 mbar, T about 230 C.). Yield: 76.0 g (280 mmol), 56%; purity: about 99.5% by .sup.1H NMR.

(9) In an analogous manner, it is possible to prepare the following compounds:

(10) TABLE-US-00001 Ex. Reactants Product Yield Type A: Monoaldehyde + monoamine + monoolefin A2 66% A3 64% A4 0 56% A5 58% A6 61% A7 63% A8 58% A9 0 55% A10 60% A11 34% A12 69% A13 67% A14 0 23% 17% Chromatographic separation of the regioisomers A15 50% A16 48% A17 68% A18 0 45% A19 65% A20 54% A21 38% A22 34% A23 00 36% A24 01 02 28% A25 03 04 32% A26 05 06 25% A27 07 08 23% A28 09 0 34% A29 45% A30 46% A31 50% A32 53% A33 0 33% A34 28% A35 23% A36 30% A37 46% A38 0 47% A39 51% A40 49% A41 47% A42 44% A43 0 43% A44 38% A45 45% A46 47% A47 48% A48 0 48% A49 50% A50 49% A51 45% A52 32% Type B: Dialdehyde + monoamine + monoolefin B1 0 30% Diastereomer mixture B2 33% Diastereomer mixture B3 30% B4 28% B5 35% Diastereomer mixture B6 0 23% Diastereomer mixture B7 25% Diastereomer mixture Type C: Trialdehyde + monoamine + monoolefin C1 Diastereomer mixture 19% Type D: Monoaldehyde + diamine + monoolefin D1 27% Diastereomer mixture D2 24% Diastereomer mixture D3 0 30% Diastereomer mixture D4 29% Diastereomer mixture D5 24% Diastereomer mixture D6 20% Diastereomer mixture D7 26% Diastereomer mixture D8 0 28% Diastereomer mixture D9 25% Diastereomer mixture Type E: Monoaldehyde + triamine + monoolefin E1 19% Diastereomer mixture Type F: Monoaldehyde + monoamine + diolefin F1 26% F2 25% F3 00 28% F4 01 02 31% F5 03 04 20% F6 05 06 25% F7 07 08 24% Type G: Monoaldehyde + monoamine + triolefin G1 09 0 13%

(11) The compounds of the A33 ff., B, D, D, E, F and G type may preferably find use as e-TMM, HBM, ETM, SMB and SEB.

Example A53

Functionalization of the Materials by Suzuki Coupling

(12) ##STR00211##

(13) A mixture of 22.5 g (50 mmol) of A49, 12.9 g (75 mmol) of 1-naphthylboronic acid, 31.8 g (150 mmol) of tripotassium phosphate, 224.5 mg (1 mmol) of palladium(II) acetate, 1.8 g (6 mmol) of tri-o-tolylphosphine, 200 mL of toluene, 50 mL of dioxane and 250 mL of water is heated under reflux with good stirring for 20 h. After cooling, the aqueous phase is removed, washed twice with 100 mL each time of water and once with 100 mL of sat. sodium chloride solution and then filtered through a Celite bed in order to remove palladium. After concentration, the residue is recrystallized five times from DMF and then fractionally sublimed twice under high vacuum (p about 10.sup.5 mbar, T: 280-300 C.). Yield: 11.2 g (22.5 mmol), 45% of theory. Purity: 99.9% by HPLC.

(14) In an analogous manner, it is possible to prepare the following compounds:

(15) TABLE-US-00002 Ex. Bromide Boronic acid Product Yield A54 64% A55 74% A56 70%

Example A57

Functionalization of the Materials by Buchwald Coupling

(16) ##STR00218##

(17) A mixture of 22.5 g (50 mmol) of A49, 22.6 g (60 mmol) of N-[1,1-biphenyl]-4-yl-9,9-dimethyl-9H-fluorene [897671-69-1], 7.2 g (75 mmol) of sodium tert-butoxide, 224.5 mg (1 mmol) of palladium(II) acetate, 263 mg (1.3 mmol) of tri-tert-butylphosphine and 300 mL of toluene is heated under reflux with good stirring for 20 h. After cooling, the reaction mixture is washed twice with 100 mL each time of water and once with 100 mL of sat. sodium chloride solution and then filtered through a Celite bed in order to remove palladium. After concentration, the residue is recrystallized five times from DMF and then fractionally sublimed twice under high vacuum (p about 10.sup.5 mbar, T: 300-310 C.). Yield: 14.3 g (19.5 mmol), 39% of theory. Purity: 99.9% by HPLC.

(18) In an analogous manner, it is possible to prepare the following compounds:

(19) TABLE-US-00003 Ex. Bromide Am ine/carbazole Product Yield A58 0 66% A59 54%

(20) Compound A1-A27 may find preferential use as bidentate chelate ligands for transition metals, for example iridium and platinum, and as electron-conducting triplex matrix material (eTMM) or electron transport material (ETM).

(21) The compounds of the A28 ff., B, D, D, E, F and G type may preferably find use as electron-conducting triplex matrix material (e-TMM), hole blocker material (HBM), electron transport material (ETM), blue singlet material (SMB) and blue singlet emitter (SEB).

Example

Production of the OLEDs

(22) 1) Vacuum-Processed Devices:

(23) OLEDs of the invention and OLEDs according to the prior art are produced by a general method according to WO 2004/058911, which is adapted to the circumstances described here (variation in layer thickness, materials used).

(24) In the examples which follow, the results for various OLEDs are presented. Glass plaques with structured ITO (50 nm, indium tin oxide) form the substrates to which the OLEDs are applied. The OLEDs basically have the following layer structure: substrate/hole transport layer 1 (HTL1) consisting of HTM doped with 3% NDP-9 (commercially available from Novaled), 20 nm/hole transport layer 2 (HTL2)/optional electron blocker layer (EBL)/emission layer (EML)/optional hole blocker layer (HBL)/electron transport layer (ETL)/optional electron injection layer (EIL) and finally a cathode. The cathode is formed by an aluminum layer of thickness 100 nm.

(25) First of all, vacuum-processed OLEDs are described. For this purpose, all the 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 (emitter) which is added to the matrix material(s) in a particular proportion by volume by co-evaporation. Details given in such a form as M3:M2:Ir(L1).sub.3 (55%:35%:10%) mean here that the material M3 is present in the layer in a proportion by volume of 55%, M2 in a proportion of 35% and Ir(L1).sub.3 in a proportion of 10%. Analogously, the electron transport layer may also consist of a mixture of two materials. The exact structure of the OLEDs can be found in Table 1. The materials used for production of the OLEDs are shown in Table 4.

(26) The OLEDs are characterized in a standard manner. For this purpose, the electroluminescence spectra, the power efficiency (measured in cd/A) and the voltage (measured at 1000 cd/m.sup.2 in V) are determined from current-voltage-brightness characteristics (IUL characteristics). For selected experiments, the lifetime is determined. The lifetime is defined as the time after which the luminance has fallen from a particular starting luminance to a certain proportion. The figure LD50 means that the lifetime specified is the time at which the luminance has dropped to 50% of the starting luminance, i.e. from, for example, 1000 cd/m.sup.2 to 500 cd/m.sup.=. According to the emission color, different starting brightnesses are used. The values for the lifetime can be converted to a figure for other starting luminances with the aid of conversion formulae known to those skilled in the art. In this context, the lifetime for a starting luminance of 1000 cd/m.sup.2 is a standard figure.

(27) Use of Compounds of the Invention in OLEDs

(28) The uses of the compounds of the invention include uses as HTM, TMM, ETM, HBM, SMB and SEB in OLEDs.

(29) TABLE-US-00004 TABLE 1 Structure of the OLED HTL2 HTL-003 HBL ETL Ex. thickness thickness EML thickness thickness thickness Use as HTM D-Vac 1 HTM A57 M1:M2:Ir-G ETM1:ETM2 220 nm 10 nm (65%:30%:5%) (50%:50%) 25 nm 20 nm D-Vac 2 HTM A58 M1:M2:Ir-G ETM1:ETM2 220 nm 10 nm (65%:30%:5%) (50%:50%) 25 nm 20 nm D-Vac 3 HTM A57 M1:M2:Ir-G A30 ETM1:ETM2 220 nm 10 nm (65%:30%:5%) 5 nm (50%:50%) 25 nm 20 nm D-Vac 4 HTM A57 M1:M2:Ir-G HBM- ETM1:ETM2 220 nm 10 nm (65%:30%:5%) Ref (50%:50%) 25 nm 5 nm 20 nm Use as TMM D-Vac 5 HTM A32:M2:Ir-G M1 ETM1:ETM2 220 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 20 nm D-Vac 5-Ref HTM TMM-Ref:M2:Ir-G M1 ETM1:ETM2 220 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 20 nm D-Vac 6 HTM A37:M2:Ir-R M1 ETM1:ETM2 220 nm (65%:30%:5%) 10 nm (50%:50%) 30 nm 20 nm D-Vac 7 HTM B3:M2:Ir-R M1 ETM1:ETM2 220 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 20 nm D-Vac 8 HTM B3:M2:Ir-R D3 ETM1:ETM2 220 nm (60%:35%:5%) 10 nm (50%:50%) 30 nm 20 nm D-Vac 9 HTM M1:A59:Ir-R D3 ETM1:ETM2 220 nm (60%:35%:5%) 10 nm (50%:50%) 30 nm 20 nm D-Vac 10 HTM F4:A59:Ir-R D3 ETM1:ETM2 220 nm (60%:35%:5%) 10 nm (50%:50%) 30 nm 20 nm Use as ETM D-Vac 11 HTM M1:M2:Ir-G M1 E1:ETM2 220 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 20 nm D-Vac 12 HTM D5:M2:Ir-R M1 E1:ETM2 220 nm (45%:50%:5%) 10 nm (50%:50%) 25 nm 20 nm Use as SEB/SMB D-Vac 13 HTM D4::SEB ETM1:ETM2 190 nm (95%:5%) (50%:50%) 20 nm 30 nm D-Vac13-Ref HTM SMB-Ref:SEB ETM1:ETM2 190 nm (95%:5%) (50%:50%) 20 nm 30 nm D-Vac 14 HTM A39:SEB ETM1:ETM2 190 nm (95%:5%) (50%:50%) 20 nm 30 nm D-Vac 15 HTM A42:SEB ETM1:ETM2 190 nm (95%:5%) (50%:50%) 20 nm 30 nm D-Vac 16 HTM SMB:A44 ETM1:ETM2 190 nm (95%:5%) (50%:50%) 20 nm 30 nm

(30) TABLE-US-00005 TABLE 2 Results for the vacuum-processed OLEDs EQE (%) Voltage (V) CIE x/y LD50 (h) Ex. 1000 cd/m.sup.2 1000 cd/m.sup.2 1000 cd/m.sup.2 1000 cd/m.sup.2 Use as HTM D-Vac 1 18.3 3.5 0.34/0.63 55000 D-Vac 2 19.4 3.5 0.34/0.64 D-Vac 3 17.6 3.6 0.35/0.64 70000 D-Vac 4 18.1 3.7 0.35/0.64 50000 Use as TMM D-Vac 5 18.8 3.6 0.35/0.64 70000 D-Vac 5-Ref 18.5 3.6 0.35/0.65 30000 D-Vac 6 16.9 3.3 0.67/0.33 85000 D-Vac 7 16.5 3.2 0.67/0.33 D-Vac 8 16.7 3.1 0.67/0.33 D-Vac 9 16.7 3.2 0.66/0.34 D-Vac 10 16.3 3.3 0.67/0.33 Use as ETM D-Vac 11 17.0 3.3 0.35/0.64 D-Vac 12 16.6 3.2 0.67/0.33 Use as SEB/SMB D-Vac 13 7.2 3.9 0.15/0.17 8000 D-Vac 13-Ref 7.0 4.2 0.15/0.17 6000 D-Vac 14 7.0 4.0 0.15/0.17 D-Vac 15 7.4 4.2 0.15/0.17 D-Vac 16 5.5 3.9 0.16/0.24

(31) 2) Solution-Processed Devices:

(32) A: From Soluble Functional Materials

(33) The iridium complexes of the invention may also be processed from solution and lead therein to OLEDs which are much simpler in terms of process technology compared to the vacuum-processed OLEDs, but nevertheless have good properties. The production of such components is based on the production of polymeric light-emitting diodes (PLEDs), which has already been described many times in the literature (for example in WO 2004/037887). The structure is composed of substrate/ITO/PEDOT (80 nm)/interlayer (80 nm)/emission layer (80 nm)/cathode. For this purpose, substrates from Technoprint (soda-lime glass) are used, to which the ITO structure (indium tin oxide, a transparent conductive anode) is applied. The substrates are cleaned in a cleanroom with DI water and a detergent (Deconex 15 PF) and then activated by a UV/ozone plasma treatment. Thereafter, likewise in the cleanroom, as a buffer layer, an 80 nm layer of PEDOT (PEDOT is a polythiophene derivative (Baytron P VAI 4083sp.) from H. C. Starck, Goslar, which is supplied as an aqueous dispersion) is applied by spin-coating. The required spin rate depends on the degree of dilution and the specific spin-coater geometry (typical value for 80 nm: 4500 rpm). In order to remove residual water from the layer, the substrates are baked on a hotplate at 180 C. for 10 minutes. The interlayer used serves for hole injection; in this case, HIL-012 from Merck is used. The interlayer may alternatively also be replaced by one or more layers which merely have to fulfill the condition of not being leached off again by the subsequent processing step of EML deposition from solution. For production of the emission layer, the emitters of the invention are dissolved together with the matrix materials in toluene. The typical solids content of such solutions is between 16 and 25 g/L when, as here, the layer thickness of 80 nm which is typical of a device is to be achieved by means of spin-coating. The solution-processed devices contain an emission layer composed of (polystyrene):matrix1:matrix2:Ir-G-Sol (25%:25%:40%:10%). The emission layer is spun on in an inert gas atmosphere, argon in the present case, and baked at 130 C. for 30 min. Lastly, a cathode composed of barium (5 nm) and then aluminum (100 nm) (high-purity metals from Aldrich, particularly barium 99.99% (cat. no. 474711); vapor deposition systems from Lesker or the like, typical vapor deposition pressure 510.sup.6 mbar) is applied by vapor deposition. It is optionally possible first to apply a hole blocker layer and then an electron transport layer and only then the cathode (e.g. Al or LiF/Al) by vapor deposition under reduced pressure. In order to protect the device from air and air humidity, the device is finally encapsulated and then characterized. The OLED examples cited are yet to be optimized; table 3 summarizes the data obtained.

(34) TABLE-US-00006 TABLE 3 Results with materials processed from solution Matrix1 EQE (%) Voltage (V) CIE x/y Ex. Matrix2 1000 cd/m.sup.2 1000 cd/m.sup.2 1000 cd/m.sup.2 Green OLEDs D-Sol1 A57 18.3 5.4 0.35/0.63 M1 D-Sol2 M2 18.6 5.7 0.34/0.64 C1

(35) TABLE-US-00007 TABLE 4 Structural formulae of the materials used 0