Materials for organic electroluminescent devices

Abstract

The present invention relates to carbazole derivatives, in particular for use as triplet matrix materials in organic electroluminescent devices. The invention further relates to a method for producing the compounds according to the invention and to electronic devices comprising same.

Claims

1. An organic electroluminescent device which comprises a compound of the formula (2a) ##STR00168## where the following applies to the symbols and indices used: Ar is on each occurrence, identically or differently, a phenylene group, which is optionally substituted by one or more radicals R; wherein the phenylene is identically or differently selected from the formulae (3), (4) or (5), ##STR00169##  where the dashed bond in each case indicates the linking of these groups and each of these groups is optionally substituted by one or more radicals R and wherein at least one of the phenylene groups is a group of formula (4) or formula (5), Ar.sup.1 is an aromatic ring system having 6 to 24 aromatic ring atoms which contains no condensed aryl groups having more than 10 aromatic ring atoms and which is optionally substituted by one or more radicals R.sup.1, or is a dibenzofuran or dibenzothiophene group, each of which is optionally substituted by one or more radicals R.sup.1; Ar.sup.2 is on each occurrence, identically or differently, an aryl group, where the aryl group has 6 to 10 aromatic ring atoms and is optionally substituted by one or more non-aromatic radicals R.sup.1, or is a dibenzofuran or dibenzothiophene group, each of which is optionally substituted by one or more radicals R.sup.1; R is on each occurrence, identically or differently, H, D, F, CN, an aryl group, a biaryl group, a triaryl group or quateraryl group, where each individual aryl group in the above-mentioned groups has 6 to 10 aromatic ring atoms and is optionally substituted by one or more radicals R.sup.1, or a carbazole group which is linked via a carbon atom and which may also be substituted by one or more radicals R.sup.1; R.sup.1 is on each occurrence, identically or differently, H, D, F, CN, a straight-chain alkyl or alkoxy group having 1 to 20 C atoms or a branched or cyclic alkyl or alkoxy group having 3 to 20 C atoms, where one or more non-adjacent CH.sub.2 groups is optionally replaced by R.sup.2C═CR.sup.2, C≡C or O and where one or more H atoms is optionally replaced by D or F, or an aryl group having 6 to 10 C atoms, which is optionally substituted by one or more radicals R.sup.2, or is a dibenzofuran or dibenzothiophene group, each of which is optionally substituted by one or more radicals R.sup.2, or a carbazole group which is linked via a carbon atom and which may also be substituted by one or more radicals R.sup.2, or an aralkyl group having 6 to 10 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.2; two adjacent substituents R.sup.1 here, together with the atoms to which they are bonded, may also form a mono- or polycyclic, aliphatic ring system with one another; R.sup.2 is on each occurrence, identically or differently, H, D or an aliphatic hydrocarbon radical having 1 to 20 C atoms or an aryl group having 6 to 10 ring atoms; n is 2, 3 or 4, wherein the compound of the formula (2a) is employed as matrix material for phosphorescent emitters in an emitting layer.

2. The organic electroluminescent device according to claim 1, wherein the group —(Ar).sub.n— is selected from the formulae (9) to (18), ##STR00170## ##STR00171## where the dashed bond in each case indicates the linking of these groups, each of these groups may also be substituted by one or more radicals R, and R and R.sup.1 have the meanings given in claim 1.

3. The organic electroluminescent device according to claim 1, wherein the radical R is selected, identically or differently on each occurrence, from the group consisting of H, D, F, CN, phenyl, biphenyl or terphenyl, where each of the aryl groups in the above-mentioned groups is optionally substituted by one or more radicals R.sup.1, and R.sup.1 stands, identically or differently on each occurrence, for H or an alkyl group having 1 to 5 C atoms; or a carbazole group which is linked via a carbon atom and which is optionally substituted by one or more radicals R.sup.1.

4. The organic electroluminescent device according to claim 1, wherein Ar.sup.1 is selected from the group consisting of phenyl, biphenyl, terphenyl or quaterphenyl, each of which is optionally substituted by one or more radicals R.sup.1.

5. The organic electroluminescent device according to claim 1, wherein Ar.sup.2 is selected, identically on each occurrence, from the group consisting of phenyl which is optionally substituted by one or more non-aromatic radicals R.sup.1.

6. The organic electroluminescent device according to claim 1, wherein the following applies to the symbols and indices: n=2 or 3; R is selected, identically or differently on each occurrence, from the group consisting of H, D, F, CN, phenyl, biphenyl or terphenyl, where each of the aryl groups is optionally substituted by one or more radicals R.sup.1, and R.sup.1 stands, identically or differently on each occurrence, for H or an alkyl group having 1 to 5 C atoms; or a carbazole group which is linked via a carbon atom and which may also be substituted by one or more radicals R.sup.1; Ar.sup.1 is selected from the group consisting of phenyl, biphenyl, terphenyl or quaterphenyl, each of which is optionally substituted by one or more radicals R.sup.1; Ar.sup.2 is selected, identically on each occurrence, from the group consisting of phenyl which is optionally substituted by one or more non-aromatic radicals R.sup.1; R.sup.1 is selected on each occurrence, identically or differently, from the group consisting of H, D, F, a straight-chain alkyl group having 1 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms, where one or more non-adjacent CH.sub.2 groups is optionally replaced by R.sup.2C═CR.sup.2 and where one or more H atoms is optionally replaced by F, or an aryl group having 6 to 10 C atoms, which is optionally substituted by one or more radicals R.sup.2, or is a dibenzofuran or dibenzothiophene group, each of which is optionally substituted by one or more radicals R.sup.2, or a carbazole group which is linked via a carbon atom and which may also be substituted by one or more radicals R.sup.2.

7. The organic electroluminescent device according to claim 1, wherein Ar is on each occurrence, identically or differently, a phenylene group, which is optionally substituted by one or more radicals R.

8. The organic electroluminescent device according to claim 1, wherein n=2 or 3.

9. The organic electroluminescent device according to claim 1, wherein Ar.sup.2 are identical.

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 corresponding CAS numbers are also given for each of the compounds known from the literature.

Example 1

2,4-Bis-(4-tert-butylphenyl)-6-chloro-1,3,5-triazine

(2) ##STR00031##

(3) 5.7 g of magnesium (234.6 mmol) are initially introduced in a 500 ml four-necked flask, and a solution of 50 g of bromo-4-tert-butylphenyl (234.6 mmol) in 200 ml of THF is slowly added dropwise. The reaction mixture is heated at the boil for 1.5 h and subsequently cooled to room temperature. Cyanogen chloride (18.8 g, 102 mmol) in 200 ml of THF is initially introduced in a second flask and cooled to 0° C. The cooled Grignard reagent is added dropwise at this temperature, and the mixture is stirred at room temperature for 12 h. After this time, 150 ml of HCl are added to the reaction mixture, and the aqueous phase is extracted three times with dichloromethane. The combined organic phases are washed with water, dried over Na.sub.2SO.sub.4 and evaporated. The residue is recrystallised from ethanol. The yield is 31 g (81.6 mmol, 80%).

Example 2

2,4-Bis(3-bromophenyl)-6-phenyl-1,3,5-triazine

(4) ##STR00032##

(5) 49 ml (392 mmol) of benzoyl chloride, 52.3 g (392 mmol) of AlCl.sub.3 and 8.5 ml of thionyl chloride are initially introduced in 500 ml of 1,2-dichlorobenzene under protective-gas atmosphere. 150 g (824 mmol) of 3-bromobenzonitrile, dissolved in 300 ml of 1,2-dichlorobenzene, are added dropwise to this solution at room temperature via a dropping funnel, the mixture is subsequently stirred at 100° C. for 1 h, then stirred at 40° C. for 18 h. After this time, 1.5 l of methanol are added to the reaction mixture, and the residue is separated. The residue is washed by stirring with hot methanol, giving 59 g (126 mmol) (32%) of the product.

Example 3

2,4-Bisbiphenyl-3-yl-6-chloro-1,3,5-triazine

(6) ##STR00033##

(7) 5.2 g of magnesium (0.215 mol) are initially introduced in a 500 ml four-necked flask, and a solution of 50 g of bromobiphenyl (214 mmol) in 200 ml of THF is slowly added dropwise. The reaction mixture is heated at the boil for 1.5 h and subsequently cooled to room temperature. Cyanogen chloride (17.2 g, 93 mmol) in 150 ml of THF is initially introduced in a second flask and cooled to 0° C. The cooled Grignard reagent then added dropwise at this temperature, and the mixture is stirred at RT for 12 h. After this time, 150 of HCl are added to the reaction mixture, and the aqueous phase is extracted three times with dichloromethane. The combined organic phases are washed with water, dried over Na.sub.2SO.sub.4 and evaporated. The residue is recrystallised from EtOH. The yield is 32.8 g (78 mmol, 84%).

Example 4

2-Chloro-4,6-bis[1,1′; 3′,1″]terphenyl-5′-yl-1,3,5-triazine

(8) ##STR00034##

(9) 3.93 g of magnesium (162 mmol) are initially introduced in a 500 ml four-necked flask, and a solution of 50 g of 5′-bromo[1,1″; 3″,1″]terphenyl (162 mmol) in 150 ml of THF is slowly added dropwise. The reaction mixture is heated at the boil for 1.5 h and subsequently cooled to room temperature. Cyanogen chloride (13 g, 70 mmol) in 150 ml of THF is initially introduced in a second flask and cooled to 0° C. The cooled Grignard reagent is added dropwise at this temperature, and the mixture is stirred at room temperature for 12 h. After this time, 150 ml of HCl are added to the reaction mixture, and the aqueous phase is extracted three times with dichloromethane. The combined organic phases are washed with water, dried over Na.sub.2SO.sub.4 and evaporated. The residue is recrystallised from EtOH. The yield is 27.8 g (49 mol, 70%).

Example 5

2-Chloro-4,6-bis(3-([3,1′; 5,1″]terphen-1-yl)phen-1-yl)-1,3,5-triazine

(10) ##STR00035##

(11) 2.0 g of magnesium (81 mmol) are initially introduced in a 500 ml four-necked flask, and a solution of 31.2 g of 5′-(3-bromophenyl)[1,1′; 3′,1″]terphenyl (81 mmol) in 100 ml of THF is slowly added dropwise. The reaction mixture is heated at the boil for 1.5 h and subsequently cooled to room temperature. Cyanogen chloride (6.4 g, 35 mmol) in 50 ml of THF is initially introduced in a second flask and cooled to 0° C. The cooled Grignard reagent is added dropwise at this temperature, and the mixture is stirred at room temperature for 12 h. After this time, 150 ml of HCl are added to the reaction mixture, the aqueous phase is extracted three times with dichloromethane. The combined organic phases are washed with water and dried over Na.sub.2SO.sub.4 and evaporated. The residue is recrystallised from toluene. The yield is 6.8 g (9.4 mmol, 28%).

Example 6

3-[3-(4,6-Diphenyl-1,3,5-triazin-2-yl)phenyl]-9-phenyl-9H-carbazole

(12) ##STR00036##

(13) 28.2 g (110.0 mmol) of (9-phenyl-9H-carbazol-3-yl)boronic acid, 42.6 g (110.0 mmol) of 2-(3-bromophenyl)-4,6-diphenyl-1.3.5-triazine and 44.6 g (210.0 mmol) of tripotassium phosphate are suspended in 500 ml of toulene, 500 ml of dioxane and 500 ml of water. 913 mg (3.0 mmol) of tri-o-tolylphosphine and then 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 dichloromethane/isopropanol and finally sublimed in a high vacuum (p=5×10.sup.−7 mbar). The purity is 99.9% (HPLC). The yield is 52 g (94 mmol), corresponding to 86% of theory.

(14) The following compounds are obtained analogously:

(15) TABLE-US-00001 Starting material 1 Starting material 2 6a 6b 0 6c 6d 6e 6f 6g 0 6h 6i 6j 6k 6l 0 6m 6n 6o 6p 6q 0 6r 6s 6t 6u Product Yield 6a 79% 6b 0 81% 6c 83% 6d 77% 6e 88% 6f 76% 6g 73% 6h 88% 6i 76% 6j 72% 6k 89% 6l 0 77% 6m 85% 6n 76% 6o 68% 6p 78% 6q 69% 6r 84% 6s 80% 6t 79% 6u 69%

Example 7

3-(5-Bromobiphenyl-3-yl)-9-phenyl-9H-carbazole

(16) ##STR00100##

(17) 15.5 g (43.3 mmol) of 3-bromo-5-iodobiphenyl and 13.7 g (48 mmol) of (9-phenyl-9H-carbazol-3-yl)boronic acid are dissolved in 80 ml of toluene and degassed. 281 ml of a degassed 2M K.sub.2CO.sub.3 solution and 2.5 g (2.2 mmol) of Pd(OAc).sub.2 are added. The reaction mixture is subsequently stirred at 80° C. for 48 h under a protective-gas atmosphere. The cooled solution is diluted with toluene, washed a number of times with water, dried and evaporated. The product is purified by column chromatography on silica gel with toluene/heptane (1:2). The purity is 98%. Yield: 17.6 g (37 mmol, 78%) of theory.

(18) The following compounds are obtained analogously:

(19) TABLE-US-00002 Starting material 1 Starting material 2 Product Yield 7a 01 02 03 70% 7b 04 05 06 69% 7c 07 08 09 68% 7d 0 83%

Example 8

3-(5-Boronobiphenyl-3-yl)-9-phenyl-9H-carbazole

(20) ##STR00113##

(21) 110 ml (276 mmol) of n-buthyllithium (2.5 M in hexane) are added dropwise to a solution, cooled to −78° C., of 128 g (270 mmol) of 3-(5-bromobiphenyl-3-yl)-9-phenyl-9-H-carbazole in 1500 ml of diethyl ether. The reaction mixture is stirred at −78° C. for 30 min. The mixture is allowed to come to room temperature, re-cooled to −78° C., and a mixture of 40 ml (351 mmol) of trimethyl borate in 50 ml of diethyl ether is then added rapidly. After warming to −10° C., the mixture is hydrolysed using 135 ml of 2 N hydrochloric acid. The organic phase is separated off, washed with water, dried over sodium sulfate and evaporated to dryness. The residue is taken up in 300 ml of n-heptane, the colourless solid is filtered off with suction, washed with n-heptane and dried in vacuo. Yield: 112 g (256 mmol), 95% of theory.

(22) The following compounds are obtained analogously:

(23) TABLE-US-00003 Starting material 1 Product Yield 8a 64% 8b 60% 8c 63% 8d 0 69% 8e 59% 8f 83% 8g 73%

Example 9

3-[3″-(4,6-Diphenyl-1,3,5-triazin-2-yl)[1,1′; 3′,1″]terphenyl-5′-yl]-9-phenyl-9H-carbazole

(24) ##STR00128##

(25) 2.47 g (8.1 mmol) of tetrakistriphenylphosphinopalladium(0) are added to a vigorously stirred suspension of 15.5 g (40 mmol) of 2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine, 17.5 g (40 mmol) of 3-(5-boronobiphenyl-3-yl)-9-phenyl-9H-carbazole and 63.9 g (127 mmol) of Na.sub.2CO.sub.3 in 500 ml of DMF, and the mixture is subsequently heated under reflux for 16 h. After cooling, the solid which has precipitated out is filtered off with suction, washed three times with 50 ml of toluene, three times with 50 ml of ethanol:water (1:1, v:v) and three times with 100 ml of ethanol and recrystallised three times from DMF (about 15 ml/g). and finally sublimed in a high vacuum (p=5×10.sup.−7 mbar). Yield 27 g (38 mmol), 85.0% of theory; purity 99.9% (HPLC)

(26) The following compounds are obtained analogously:

(27) TABLE-US-00004 Starting material 1 Starting material 2 9a 0 9b 9c 9d 9e 9f 0 9g 9h 9i Product Yield 9a 86% 9b 67% 9c 69% 9d 0 76% 9e 82% 9f 80% 9g 64% 9h 73% 9i 71%

Example

Production of OLEDs

(28) 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).

(29) 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/hole-transport layer (HTL)/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 3. Furthermore, a reference such as “6a” here relates to the material mentioned in Example 6a described above. This also applies analogously to all other compounds according to the invention.

(30) 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 H1:VCbz1:TEG1 (55%:35%:10%) here means that material H1 is present in the layer in a proportion by volume of 55%, VCbz1 is present in the layer in a proportion of 35% 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.

(31) 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. The lifetime LT is defined as the time after which the luminous density drops to a certain proportion L1 from the initial luminous density L0 on operation at constant current. An expression of L0=10000 cd/m.sup.2 and L1=80% in Table X2 means that the lifetime indicated in column LT corresponds to the time after which the initial luminous density drops from 10000 cd/m.sup.2 to 8000 cd/m.sup.2.

(32) The data of the various OLEDs are summarised in Table 2. Example V1-V6 are OLEDs comprising materials in accordance with the prior art, Examples E1-E17 show data of OLEDs comprising materials according to the invention.

(33) 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, improvements compared with the prior art are also achieved on use of the compounds according to the invention which are not described in greater detail, in some cases in all parameters, but in some cases only an improvement of efficiency or voltage or lifetime is observed. However, even the improvement of one of the said parameters represents a significant advance, since various applications require optimisation with respect to different parameters.

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

(35) In combination with the green-emitting dopant TEG1, materials according to the invention exhibit significant improvements compared with the prior art. A power efficiency which is improved by up to 15% (Examples V1 and E3) and a 40% better lifetime (Examples V2 and E3) are obtained.

(36) If two materials are used as a mixture with dopant TEG1 in the EML, a lifetime which is improved by about 30% and an approximately 20% higher power efficiency are obtained with material 6n according to the invention in combination with VCbz1 compared with the use of H2 with VCbz1 (Examples V4 and E10).

(37) Similarly good improvements are also obtained on use of the red-emitting dopant TER1 (Examples V6 and E17).

(38) The materials according to the invention thus give rise to significant improvements compared with the prior art on use as matrix materials in phosphorescent OLEDs.

(39) Use of Compounds According to the Invention as Electron-Transport Materials

(40) On use of compound 6n according to the invention as electron-transport material, significantly lower voltage and better efficiency are obtained than with substance H3 in accordance with the prior art (Examples V5 and E16).

(41) TABLE-US-00005 TABLE 1 Structure of the OLEDs HTL IL EBL RBL EIL Thick- Thick- Thick- EML Thick- ETL Thick- Ex. ness ness ness Thickness ness Thickness ness V1 SpA1 HATCN SpMA1 H1:TEG1 (90%:10%) — ST1:LiQ (50%:50%) — 70 nm 5 nm 90 nm 30 nm 40 nm V2 SpA1 HATCN SpMA1 H2:TEG1 (90%:10%) — ST1:LiQ (50%:50%) — 70 nm 5 nm 90 nm 30 nm 40 nm V3 SpA1 HATCN SpMA1 H3:TEG1 (90%:10%) — ST1:LiQ (50%:50%) — 70 nm 5 nm 90 nm 30 nm 40 nm V4 SpA1 HATCN SpMA1 H2:VCbz1:TEG1 IC1 ST1:LiQ (50%:50%) — 70 nm 5 nm 90 nm (45%:45%:10%) 30 nm 10 nm 30 nm V5 SpA1 HATCN SpMA1 IC1:TEG1 (90%:10%) — H3 LiQ 70 nm 5 nm 90 nm 30 nm 40 nm 3 nm V6 SpA1 HATCN SpMA1 H1:TER1 — ST1:LiQ (50%:50%) — 90 nm 5 nm 130 nm  (92%:8%) 40 nm 40 nm E1 SpA1 HATCN SpMA1 6:TEG1 (90%:10%) — ST1:LiQ (50%:50%) — 70 nm 5nm 90 nm 30 nm 40 nm E2 SpA1 HATCN SpMA1 6a:TEG1 (90%:10%) — ST1:LiQ (50%:50%) — 70 nm 5 nm 90 nm 30 nm 40 nm E3 SpA1 HATCN SpMA1 6b:TEG1 (90%:10%) — ST1:LiQ (50%:50%) — 70 nm 5 nm 90 nm 30 nm 40 nm E4 SpA1 HATCN SpMA1 6e:TEG1 (90%:10%) — ST1:LiQ (50%:50%) — 70 nm 5 nm 90 nm 30 nm 40 nm E5 SpA1 HATCN SpMA1 6f:TEG1 (90%:10%) — ST1:LiQ (50%:50%) — 70 nm 5 nm 90 nm 30 nm 40 nm E6 SpA1 HATCN SpMA1 6h:TEG1 (90%:10%) — ST1:LiQ (50%:50%) — 70 nm 5 nm 90 nm 30 nm 40 nm E7 SpA1 HATCN SpMA1 6j:TEG1 (90%:10%) — ST1:LiQ (50%:50%) — 70 nm 5 nm 90 nm 30 nm 40 nm E8 SpA1 HATCN SpMA1 6k:TEG1 (90%:10%) — ST1:LiQ (50%:50%) — 70 nm 5 nm 90 nm 30 nm 40 nm E9 SpA1 HATCN SpMA1 6n:TEG1 (90%:10%) — ST1:LiQ (50%:50%) — 70 nm 5 nm 90 nm 30 nm 40 nm E10 SpA1 HATCN SpMA1 6n:VCbz1:TEG1 IC1 ST1:LiQ (50%:50%) — 70 nm 5 nm 90 nm (45%:45%:10%) 30 nm 10 nm 30 nm E11 SpA1 HATCN SpMA1 6o:TEG1 (90%:10%) — ST1:LiQ (50%:50%) — 70 nm 5 nm 90 nm 30 nm 40 nm E12 SpA1 HATCN SpMA1 6p:TEG1 (90%:10%) — ST1:LiQ (50%:50%) — 70 nm 5 nm 90 nm 30 nm 40 nm E13 SpA1 HATCN SpMA1 9:TEG1 (90%:10%) — ST1:LiQ (50%:50%) — 70nm 5 nm 90 nm 30 nm 40 nm E14 SpA1 HATCN SpMA1 9f:TEG1 (90%:10%) — ST1:LiQ (50%:50%) — 70 nm 5 nm 90 nm 30 nm 40 nm E15 SpA1 HATCN SpMA1 9h:TEG1 (90%:10%) — ST1:LiQ (50%:50%) — 70 nm 5 nm 90 nm 30 nm 40 nm E16 SpA1 HATCN SpMA1 IC1:TEG1 (90%:10%) — 6n LiQ 70 nm 5 nm 90 nm 30 nm 40 nm 3 nm E17 SpA1 HATCN SpMA1 6n:TER1 — ST1:LiQ (50%:50%) — 90 nm 5 nm 130 nm  (92%:8%) 40 nm 40 nm

(42) TABLE-US-00006 TABLE 2 Data of the OLEDs U1000 CE1000 PE1000 EQE CIE x/y at L1 LT Ex. (V) (cd/A) (Im/W) 1000 1000 cd/m.sup.2 L0 % (h) V1 4.0 55 43 15.3% 0.33/0.62 10000 80 65 cd/m.sup.2 V2 4.1 44 34 12.3% 0.32/0.62 10000 80 110 cd/m.sup.2 V3 4.9 56 36 15.6% 0.33/0.62 10000 80 105 cd/m.sup.2 V4 4.0 50 39 13.8% 0.33/0.62 10000 80 240 cd/m.sup.2 V5 4.4 53 38 14.7% 0.33/0.62 10000 80 90 cd/m.sup.2 V6 4.6 9.3 6.4  9.8% 0.67/0.33  4000 80 290 cd/m.sup.2 E1 4.2 56 42 15.5% 0.32/0.62 10000 80 85 cd/m.sup.2 E2 4.2 55 41 15.3% 0.33/0.63 10000 80 115 cd/m.sup.2 E3 3.7 59 50 16.5% 0.32/0.62 10000 80 155 cd/m.sup.2 E4 4.4 54 39 15.0% 0.33/0.62 10000 80 130 cd/m.sup.2 E5 4.1 58 44 16.1% 0.33/0.62 10000 80 120 cd/m.sup.2 E6 4.3 51 38 14.3% 0.33/0.62 10000 80 110 cd/m.sup.2 E7 4.0 57 45 15.9% 0.33/0.62 10000 80 135 cd/m.sup.2 E8 4.8 53 35 14.8% 0.33/0.63 10000 80 90 cd/m.sup.2 E9 4.0 60 47 16.8% 0.33/0.62 10000 80 140 cd/m.sup.2 E10 3.8 57 47 15.8% 0.33/0.62 10000 80 305 cd/m.sup.2 E11 4.2 59 44 16.4% 0.33/0.62 10000 80 140 cd/m.sup.2 E12 4.1 57 44 15.9% 0.32/0.63 10000 80 110 cd/m.sup.2 E13 4.1 59 45 16.3% 0.33/0.62 10000 80 130 cd/m.sup.2 E14 3.7 55 46 15.2% 0.33/0.62 10000 80 105 cd/m.sup.2 E15 4.2 60 45 16.6% 0.33/0.62 10000 80 135 cd/m.sup.2 E16 3.2 59 58 16.5% 0.33/0.62 10000 80 110 cd/m.sup.2 E17 4.5 10.8 7.6 11.7% 0.67/0.33  4000 80 360 cd/m.sup.2

(43) TABLE-US-00007 TABLE 3 Structural formulae of the materials for the OLEDs HATCN SpA1 IC1 ST1 0 LiQ TEG1 SpMA1 TER1 VCbz1 H1 (prior art) H2 (prior art) H3 (prior art)