Materials for organic electroluminescent devices

Abstract

The present invention relates to compounds according to formula (1) and formula (2), said compounds being suitable for use in electronic devices, in particular organic electroluminescent devices.

Claims

1. A compound of the formula (4), (5), (7), (8), and (19-(22) ##STR00164## ##STR00165## where the following applies to the symbols and indices used: X is on each occurrence, identically or differently, CR; or X stands for C if a group L is bonded to this group X; Y, Y.sup.1, Y.sup.2 and Y.sup.3 is on each occurrence, identically or differently, C(R.sup.1).sub.2; Z is on each occurrence, identically or differently, CR or N; or Z stands for C if a group Y.sup.1 or Y.sup.2 or Y.sup.3 is bonded to this group Z; a group R is replaced by L in the formula (7) and (8) if the group L is bonded in the corresponding carbon atom, L is, identically or differently, R if q=1 or is a di-, tri-, tetra-, penta- or hexavalent straight-chain alkylene, alkylidene, alkyleneoxy or thioalkyleneoxy group having 1 to 40 C atoms or a branched or cyclic alkylene, alkylidene, alkyleneoxy or thioalkyleneoxy group having 3 to 40 C atoms or an alkenylene or alkynylene group having 2 to 40 C atoms, which may be substituted by in each case one or more radicals R.sup.2, where in each case one or more non-adjacent CH.sub.2 groups may be replaced by R.sup.2CCR.sup.2, CC, Si(R.sup.2).sub.2, CO, CNR.sup.2, P(O)R.sup.2, SO, SO.sub.2, O, S or CONR.sup.2 and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, or a di-, tri-, tetra-, penta- or hexavalent aromatic ring system having 5 to 40, aromatic ring atoms, which may be substituted by one or more radicals R.sup.2, or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which contains, as heteroaryl groups, exclusively sulfur-containing or oxygen-containing heteroaryl groups and which may be substituted by one or more radicals R.sup.2, or P(R.sup.2).sub.3-r, P(O)(R.sup.2).sub.3-r, C(R.sup.2).sub.4-r, Si(R.sup.2).sub.4-r, N(Ar).sub.3-r, where r stands for 2, 3 or 4, with the proviso that r is not greater than the maximum valence of L; or L is a chemical bond, in which case q=2; the valence of the group L=q+1 here; q is 1, 2, 3, 4, 5 or 6; R and R.sup.1 is selected on each occurrence, identically or differently, from the group consisting of H, D, F, Cl, Br, I, CN, NO.sub.2, C(O)Ar, C(O)R.sup.2, P(O)(Ar).sub.2, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms, each of which may be substituted by one or more radicals R.sup.2, where one or more non-adjacent CH.sub.2 groups may be replaced by R.sup.2CCR.sup.2, Si(R.sup.2).sub.2, C0, CNR.sup.2, P(O)(R.sup.2), SO, SO.sub.2, NR.sup.2, O, S or CONR.sup.2 and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, an aromatic ring system having 6 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.2, a heteroaromatic ring system having 5 to 60 aromatic ring atoms, which contains, as heteroaryl groups, sulfur-containing or oxygen-containing heteroaryl groups and which may be substituted by one or more radicals R.sup.2, an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R.sup.2, or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R.sup.2, where two substituents R.sup.1 which are bonded in the same group Y may optionally form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system with one another, which may be substituted by one or more radicals R.sup.2; furthermore, two adjacent radicals R may form a condensed-on benzo ring, which may be 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, F, Cl, Br, I, CN, NO.sub.2, C(O)Ar, C(O)R.sup.3, P(O)(Ar).sub.2, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms, each of which may be substituted by one or more radicals R.sup.3, where one or more non-adjacent CH.sub.2 groups may be replaced by R.sup.3CCR.sup.3, CC, Si(R.sup.3).sub.2, CO, CNR.sup.3, P(O)(R.sup.3), SO, SO.sub.2, NR.sup.3, O, S or CONR.sup.3 and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, an aromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.3, an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R.sup.3, or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms; Ar is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5-30 aromatic ring atoms, which may be substituted by one or more non-aromatic radicals R.sup.3; two radicals Ar which are bonded to the same P atom may also be bridged to one another here by a single bond or a bridge selected from N(R.sup.3), C(R.sup.3).sub.2, O or S; R.sup.3 is selected from the group consisting of H, D, F, CN, an aliphatic hydrocarbon radical having 1 to 20 C atoms or an aromatic ring system having 5 to 30 aromatic ring atoms, in which one or more H atoms may be replaced by D, F, Cl, Br, I or CN the following compound is excluded from the invention: ##STR00166##

2. The compound according to claim 1, wherein the compound is a compound of the formula (4a) or (5a), ##STR00167## where the symbols and indices used have the meanings given in claim 1.

3. The compound according to claim 1, wherein the compound is a compound of the formulae (19a) to (22a), (24) or (25), ##STR00168## ##STR00169## where the symbols used have the meanings given under claim 1.

4. The compound according to claim 1, wherein the compound is a compound of the formulae (19b) to (22b), (24a) or (25a), ##STR00170## ##STR00171## where the symbols used have the meanings given in claim 1.

5. The compound according to claim 1, wherein R, if R stands for an aromatic or heteroaromatic ring system, is selected from the groups of the formulae (26) to (58), ##STR00172## ##STR00173## ##STR00174## ##STR00175## ##STR00176## ##STR00177## where the dashed bond indicates the bonding to the basic structure and the groups may be substituted by one or more radicals R.sup.2.

6. A process for the preparation of the compound according to claim 1, comprising the reaction steps: a) synthesis of the corresponding basic structure which does not yet contain a bridge Y; and b) introducing the group Y.

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

8. A formulation comprising at least one compound according to claim 1 and one or more solvents.

9. The formulation as claimed in claim 8, wherein the formulation is a solution, a suspension or a miniemulsion.

10. An electronic device which comprises the compound according to claim 1.

11. The electronic device as claimed in claim 10, wherein the device is selected from the group consisting of organic electroluminescent devices, organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic solar cells, organic dye-sensitised solar cells, organic optical detectors, organic photoreceptors, organic field-quench devices, light-emitting electrochemical cells, organic laser diodes and organic plasmon emitting devices.

12. An organic electroluminescent device comprising the compound according to claim 1 is employed as matrix material for fluorescent or phosphorescent emitters and/or in an electron-blocking or exciton-blocking layer and/or in a hole-transport or hole-injection layer.

Description

EXAMPLES

(1) The following syntheses are carried out, unless indicated otherwise, in dried solvents under a protective-gas atmosphere. The solvents and reagents can be purchased, for example, from Sigma-ALDRICH or ABCR. The starting material used can be, for example, phenazine. The numbers in square brackets in the case of the starting materials known from the literature relate to the CAS numbers.

Example 1: 5,10-Dihydrophenazine

(2) ##STR00043##

(3) 20 g (110 mmol) of phenazine are suspended in 600 ml of ethanol under protective gas. The reaction mixture is heated under reflux. 38.3 g (220 mmol) of sodium dithionite dissolved in 600 ml of degassed water are subsequently added dropwise, and the mixture is heated under reflux for a further 4 h. After cooling, the precipitated yellow solid is filtered off under protective gas and dried in vacuo. The purity is 92.0%. Yield: 19 g (107 mmol) 96% of theory.

Example 2: 5-Biphenyl-4-yl-10-(2-bromophenyl)-5,10-dihydrophenazine

(4) ##STR00044##

(5) 15.8 g (87.8 mmol) of 9,10-dihydrophenazine, 20 g (87 mmol) of 4-bromobiphenyl and 0.8 g (0.88 mmol) of tris(dibenzylideneacetone)dipalladium, 1.79 g (7.9 mmol) of palladium acetate are suspended in 500 ml of toluene under protective gas. The reaction mixture is heated under reflux for 8 h. 24.8 g (87 mmol) of 1-bromo-2-iodobenzene is subsequently added, and the mixture is heated under reflux for a further 8 h. After cooling, the organic phase is separated off, washed three times with 200 ml of water each time and subsequently evaporated to dryness. The product is purified by column chromatography on silica gel with toluene/heptane (1:2). The purity is 97.0%. Yield: 29 g (37 mmol) 70% of theory.

(6) Compounds 2a-2m are obtained analogously:

(7) TABLE-US-00001 Starting Starting Ex. material 1 material 2 Product Yield 2a [103068-20-8] 65% 2b 0 66% 2c [2052-07-5] 73% 2d 2f [586-78-7] 75% 2g 0 [610-94-6] 65% 2h 87% 2i 63% 2j 0 [727408-92-6] 72% 2k [86-76-0] 67% 2l [22439-61-8] 69% 2m [10016-52-1] 0 63%

(8) Compound 2n is obtained analogously:

(9) TABLE-US-00002 Starting Starting Starting Ex. material 1 material 2 material 3 Product Yield 2n [19029-32-4] 69%

Example 3: 8-Biphenyl-4-yl-8H-8,12b-diazabenzo[a]aceanthrylene

(10) ##STR00085##

(11) 73 g (0.175 mmol) of 5-biphenyl-4-yl-10-(2-bromophenyl)-5,10-dihydrophenazine are dissolved in 500 ml of dimethylacetamide under protective gas. 2.4 g (6.5 mmol) of tricyclohexylphosphine tetrafluoroborate and 701 mg (3.1 mmol) of Pd(OAc).sub.2 are added to this solution. The mixture is subsequently stirred at 120 C. for 9 h. After this time, the reaction mixture is cooled to room temperature and extracted with dichloromethane. The combined organic phases are dried over Na.sub.2SO.sub.4 and evaporated. The residue is extracted with hot toluene, recrystallised from toluene and finally sublimed in a high vacuum. The yield is 49 g (121 mmol), 81% of theory.

(12) Compounds 3a-3m are obtained analogously:

(13) TABLE-US-00003 Starting Ex. material 1 Product Yield 3a 75% 3b 76% 3c 0 73% 3e 40% 3g 76% 3h 31% 3i 29% 3j 00 01 20% 3k 02 03 71% 3l 04 05 69% 3m 06 07 72%

Example 4: 2-[2-(10-Biphenyl-2-yl-10H-phenazin-5-yl)phenyl]propan-2-ol

(14) ##STR00108##

(15) 99 g (213 mmol) of methyl 2-(10-biphenyl-2-yl-10H-phenazin-5-yl)benzoate are dissolved in 1500 ml of dried THF and degassed. The mixture is cooled to 78 C., and 569 ml (854 mmol) of methyllithium are added over the course of 40 min. The mixture is allowed to warm to 40 C. over the course of 1 h, and the reaction is monitored by TLC. When the reaction is complete, the mixture is carefully quenched with MeOH at 30 C. The reaction solution is evaporated to , and 1 l of CH.sub.2Cl.sub.2 is added, the mixture is washed, and the organic phase is dried over MgSO.sub.4 and evaporated. The yield is 90 g (194 mmol) 90% of theory.

(16) Compounds 4a-4c are obtained analogously

(17) TABLE-US-00004 Starting Ex. material 1 Product Yield 4a 09 0 87% 4b 67% 4c 74%

Example 5: 5-Biphenyl-2-yl-9,9-dimethyl-5H,9H-5,13b-diazanaphtho[3,2,1-de]anthracene

(18) ##STR00115##

(19) 20 g (43.6 mmol) of 2-[2-(10-biphenyl-2-yl-10H-phenazin-5-yl)phenyl]propan-2-ol are dissolved in 1200 ml of degassed toluene, and a suspension of 40 g of polyphosphoric acid and 28 ml of methanesulfonic acid is added, and the mixture is heated at 60 C. for 1 h. The batch is cooled, and water is added. A solid precipitates out, which is dissolved in CH.sub.2Cl.sub.2/THF (1:1). The solution is carefully rendered alkaline using 20% NaOH, the phases are separated and dried over MgSO.sub.4. The residue is extracted with hot toluene, recrystallised from toluene/heptane (1:2) and finally sublimed in a high vacuum. The yield is 15.6 g (34 mmol), 80% of theory.

(20) Compounds 5a-5d are obtained analogously:

(21) TABLE-US-00005 Starting Ex. material 1 Product Yield 5a 43% 5b 33% 5c 0 68% 5d 69%

Example 6: 1-Nitro-10-(2-bromophenyl)-10H-phenoxazine

(22) ##STR00124##

(23) 20 g (88 mmol) of 1-nitro-10H-phenoxazine (CAS: 26103-27-5), 20 g (88 mmol) of 1,2-dibromobenzene, 0.8 g (0.88 mmol) of tris(dibenzylideneacetone)dipalladium and 1.79 g (7.9 mmol) of palladium acetate are suspended in 500 ml of toluene under protective gas. The reaction mixture is heated under reflux for 8 h. After cooling, the organic phase is separated off, washed three times with 200 ml of water and subsequently evaporated to dryness. The product is purified by column chromatography on silica gel with toluene/heptane (1:2). The purity is 97.0%. Yield: 19 g (49 mmol), 78% of theory.

(24) Compounds 6a-6b are obtained analogously:

(25) TABLE-US-00006 Starting Ex. material 1 Product Yield 6a [1747-87-1] 65% 6b [61-62-5 68%

Example 7: 10-(2-Bromophenyl)-10H-phenoxazin-1-ylamine

(26) ##STR00129##

(27) 14.5 g (42 mmol) of 1-nitro-10-(2-bromophenyl)-10H-phenoxazine is suspended in 200 ml of ethanol. 26 g (140 mmol) of SnCl.sub.2 dissolved in 25 ml of conc. HCl are added in portions at 60 C. with stirring, and the mixture is heated under reflux for 8 h. The precipitate is then filtered off and dried in vacuo. The purity is 94%. Yield: 12 g (35 mmol), 92% of theory.

(28) Compounds 7a-7b are obtained analogously:

(29) TABLE-US-00007 Starting Ex. material 1 Product Yield 7a 0 89% 7b 81%

Example 8: 9-Phenyl-9H-5-oxa-9,13b-diazanaphtho[3,2,1-de]anthracene

(30) ##STR00134##

(31) 9.2 g (26.3 mmol) of 9,10-dihydrophenazine, 0.24 g (0.26 mmol) of tris(dibenzylideneacetone)dipalladium and 0.53 g (2.37 mmol) of palladium acetate are suspended in 150 ml of toluene under protective gas. The reaction mixture is heated under reflux for 8 h. 4 g (26 mmol) of 4-bromobenzene are subsequently added, and the mixture is heated under reflux for a further 8 h. After cooling, the organic phase is separated off, washed three times with 80 ml of water and subsequently evaporated to dryness. The residue is extracted with hot toluene, recrystallised from toluene/heptane (1:2) and finally sublimed in a high vacuum. The purity is 97.0%. Yield: 5.6 g (16.3 mmol) 63% of theory.

(32) Compounds 8a-8f are obtained analogously:

(33) TABLE-US-00008 Starting Starting Ex. material 1 material 2 Product Yield 8a 64% 8b [103068-20-8] 0 59% 8c 53% 8e 58% 8f [89827-45-2] 55%

Example 9: Production of OLEDs

(34) 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).

(35) The data for various OLEDs are presented in the following Examples V1 to E17 (see Tables 1 and 2). Glass plates coated with structured ITO (indium tin oxide) in a thickness of 50 nm are coated with 20 nm of PEDOT:PSS (poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate), purchased as CLEVIOS P VP AI 4083 from Heraeus Precious Metals GmbH, Germany, applied by spin coating from aqueous solution) for improved processing. These coated glass plates form the substrates to which the OLEDs are applied. The OLEDs have in principle the following layer structure: substrate/optional hole-injection layer (HIL)/hole-transport layer (HTL)/optional interlayer (IL)/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 cathode 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 1. Furthermore, a reference to the materials such as 3f relates to the material whose synthesis is described in Example 3f indicated above. This applies analogously to the other compounds according to the invention.

(36) 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), which is admixed with the matrix material or materials in a certain proportion by volume by co-evaporation. An expression such as IC1:3k:TEG1 (70%:25%:5%) here means that material IC1 is present in the layer in a proportion by volume of 70%, the material from Example 3k is present in the layer in a proportion of 25% by vol. and TEG1 is present in the layer in a proportion of 15% by vol. Analogously, the electron-transport layer may also consist of a mixture of two materials.

(37) 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), assuming Lambert emission characteristics, 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 efficiencies achieved at 1000 cd/m.sup.2, Finally, EQE1000 denotes the external quantum efficiency at an operating luminous density of 1000 cd/m.sup.2.

(38) The data of the various OLEDs are summarised in Table 2. Example V1-V3 are comparative examples in accordance with the prior art, Examples E1-E17 show data of OLEDs comprising materials according to the invention.

(39) 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.

(40) Use of Compounds According to the Invention as Hole-Transport Materials

(41) If compound 3f according to the invention is used instead of the similar compound H3 in accordance with the prior art as hole-transport material in an OLED comprising the green dopant TEG1, a virtually 20% better power efficiency is obtained (Examples V1 and E5).

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

(43) The use of two materials as matrix (host) in OLEDs comprising green-phosphorescent dopants frequently gives rise to better performance data than on use of a single material, which is why materials are of great interest for this application. Inter alia, materials according to the invention containing sulfur- or oxygen-containing heteroaromatic ring systems as substituent are distinguished here compared with triazine-containing materials in accordance with the prior art: better quantum and power efficiency (Examples V2, V3, E6, E7 and E8) are obtained. Furthermore, the lifetime is significantly improved. While the luminous density drops to 70% from its initial value of 10000 cd/m.sup.2 within 160 h and 180 h respectively for Examples V2 and V3 on operation at constant current density, this takes 300 h, 245 h and 230 h in Examples E6, E7 and E8 respectively.

(44) TABLE-US-00009 TABLE 1 Structure of the OLEDs HIL HTL IL EBL EML HBL ETL EIL Thick- Thick- Thick- Thick- Thick- Thick- Thick- Thick- Ex. ness ness ness ness ness ness ness ness V1 SpA1 HATCN H3 IC1:TEG1 ST1:LiQ 70 nm 5 nm 90 nm (90%:10%) (50%:50%) 30 nm 40 nm V2 SpA1 HATCN SpMA1 IC1:H1:TEG1 IC1 ST1:LiQ 70 nm 5 nm 90 nm (70%:25%:5%) 10 nm (50%:50%) 30 nm 30 nm V3 SpA1 HATCN SpMA1 IC1:H2:TEG1 IC1 ST1:LiQ 70 nm 5 nm 90 nm (70%:25%:5%) 10 nm (50%:50%) 30 nm 30 nm E1 SpA1 HATCN SpMA1 IC5:3c:TER1 ST2:LiQ 90 nm 5 nm 130 nm (43%:50%:7%) (50%:50%) 40 nm 40 nm E2 SpA1 HATCN SpMA1 IC5:3i:TER1 ST2:LiQ 90 nm 5 nm 130 nm (33%:60%:7%) (50%:50%) 40 nm 40 nm E3 SpA1 HATCN SpMA1 IC5:5:TER1 ST2:LiQ 90 nm 5 nm 130 nm (43%:50%:7%) (50%:50%) 40 nm 40 nm E4 SpA1 HATCN SpMA1 IC5:5d:TER1 IC1 ST2:LiQ 90 nm 5 nm 130 nm (53%:40%:7%) 10 nm (50%:50%) 40 nm 30 nm E5 SpA1 HATCN 3m IC1:TEG1 ST1:LiQ 70 nm 5 nm 90 nm (90%:10%) (50%:50%) 30 nm 40 nm E6 SpA1 HATCN SpMA1 IC1:3k:TEG1 IC1 ST1:LiQ 70 nm 5 nm 90 nm (70%:25%:5%) 10 nm (50%:50%) 30 nm 30 nm E7 SpA1 HATCN SpMA1 IC1:3l:TEG1 IC1 ST1:LiQ 70 nm 5 nm 90 nm (70%:25%:5%) 10 nm (50%:50%) 30 nm 30 nm E8 SpA1 HATCN SpMA1 IC1:3m:TEG1 IC1 ST1:LiQ 70 nm 5 nm 90 nm (70%:25%:5%) 10 nm (50%:50%) 30 nm 30 nm E9 HATCN 3a HATCN SpMA1 M2:D1 ST1:LiQ LiQ 5 nm 140 nm 5 nm 20 nm (95%:5%) (50%:50%) 1 nm 20 nm 30 nm E10 HATCN 5a HATCN SpMA1 M2:D1 ST1:LiQ LiQ 5 nm 140 nm 5 nm 20 nm (95%:5%) (50%:50%) 1 nm 20 nm 30 nm E11 5c HATCN SpMA1 IC1:TEG1 ST1:LiQ 70 nm 5 nm 90 nm (90%:10%) (50%:50%) 30 nm 40 nm E12 HATCN 8a HATCN SpMA1 M2:D1 ST1:LiQ LiQ 5 nm 140 nm 5 nm 20 nm (95%:5%) (50%:50%) 1 nm 20 nm 30 nm E13 HATCN 8b HATCN SpMA1 M2:D1 ST1:LiQ LiQ 5 nm 140 nm 5 nm 20 nm (95%:5%) (50%:50%) 1 nm 20 nm 30 nm E14 HATCN 8c HATCN SpMA1 M2:D1 ST1:LiQ LiQ 5 nm 140 nm 5 nm 20 nm (95%:5%) (50%:50%) 1 nm 20 nm 30 nm E15 HATCN 8d HATCN SpMA1 M2:D1 ST1:LiQ LiQ 5 nm 140 nm 5 nm 20 nm (95%:5%) (50%:50%) 1 nm 20 nm 30 nm E16 8b HATCN SpMA1 IC1:TEG1 ST1:LiQ 70 nm 5 nm 90 nm (90%:10%) (50%:50%) 30 nm 40 nm

(45) TABLE-US-00010 TABLE 2 Data of the OLEDs U1000 CE1000 PE1000 EQE CIE x/y at Ex. (V) (cd/A) (lm/W) 1000 1000 cd/m.sup.2 V1 3.7 55 47 15.3% 0.33/0.62 V2 3.7 53 45 14.8% 0.33/0.62 V3 3.8 45 37 12.7% 0.32/0.61 E1 4.7 10.8 7.2 11.7% 0.67/0.33 E2 5.1 11.7 7.2 12.6% 0.67/0.33 E3 4.9 10.4 6.7 11.3% 0.67/0.33 E4 4.7 10.0 6.7 10.8% 0.67/0.33 E5 3.4 59 55 16.5% 0.33/0.62 E6 3.9 57 46 15.8% 0.33/0.62 E7 3.5 60 53 16.7% 0.33/0.62 E8 3.6 56 49 16.0% 0.31/0.61 E9 4.3 9.5 6.9 7.4% 0.14/0.15 E10 4.4 10.2 7.2 7.8% 0.14/0.16 E11 3.6 57 51 16.1% 0.32/0.62 E12 4.5 10.1 7.1 7.8% 0.14/0.16 E13 4.1 9.1 6.9 7.0% 0.14/0.16 E14 4.2 10.5 7.8 8.1% 0.14/0.16 E15 4.3 9.5 7.0 7.3% 0.14/0.16 E16 3.5 58 52 15.8% 0.33/0.62

(46) TABLE-US-00011 TABLE 3 Structural formulae of the materials for the OLEDs 0 HATCN SpA1 M2 D1 TER1 ST1 LiQ TEG1 IC1 IC5 0 SpMA1 H1 (prior art) H2 (prior art) H3 (prior art)