Materials for organic electroluminescent devices

Abstract

The invention relates to compounds which are suitable for use in electronic devices, and electronic devices, in particular organic electroluminescent devices, containing said compounds.

Claims

1. A compound of formula (3) ##STR00312## where the symbols and indices used are as follows: X is the same or different at each instance and is CR.sup.1 or N; or two adjacent Xs are a group of the following formula (4), (5) or (6): ##STR00313## where {circumflex over ( )} indicates the corresponding adjacent X groups in the formula (2) or (3); V is the same or different at each instance and is C(R.sup.1).sub.2, NR.sup.1, O, S, BR.sup.1, Si(R.sup.1).sub.2 or C═O; Z is the same or different at each instance and is CR.sup.1 or N; Ar is the same or different at each instance and is an aromatic ring system which has 6 to 40 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals, or a heteroaromatic ring system which has 5 to 40 aromatic ring atoms, does not contain any electron-deficient heteroaryl groups and may be substituted by one or more R.sup.2 radicals; R, R.sup.1 is the same or different at each instance and is selected from the group consisting of H, D, F, Cl, Br, I, CN, NO.sub.2, N(Ar.sup.1).sub.2, N(R.sup.3).sub.2, C(═O)Ar.sup.1, C(═O)R.sup.3, P(═O)(Ar.sup.1).sub.2, P(Ar.sup.1).sub.2, B(Ar.sup.1).sub.2, Si(Ar.sup.1).sub.3, Si(R.sup.3).sub.3, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, each of which may be substituted by one or more R.sup.3 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by R.sup.3C═CR.sup.3, Si(R.sup.3).sub.2, C═O, C═S, C═NR.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 hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and may be substituted in each case by one or more R.sup.3 radicals, an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.3 radicals, or an aralkyl or heteroaralkyl group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.3 radicals; at the same time, it is optionally possible for two R.sup.1 substituents bonded to the same carbon atom to form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system which may be substituted by one or more R.sup.3 radicals; R.sup.2 is the same or different at each instance and is selected from the group consisting of H, D, F, Cl, Br, I, CN, NO.sub.2, N(Ar.sup.1).sub.2, N(R.sup.3).sub.2, C(═O)Ar.sup.1, C(═O)R.sup.3, P(═O)(Ar.sup.1).sub.2, P(Ar.sup.1).sub.2, B(Ar.sup.1).sub.2, Si(Ar.sup.1).sub.3, Si(R.sup.3).sub.3, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, each of which may be substituted by one or more R.sup.3 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by R.sup.3C═CR.sup.3, Si(R.sup.3).sub.2, C═O, C═S, C═NR.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 hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms, does not contain any electron-deficient heteroaryl groups and may be substituted in each case by one or more R.sup.3 radicals, an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms, does not contain any electron-deficient heteroaryl groups and may be substituted by one or more R.sup.3 radicals, or an aralkyl or heteroaralkyl group which has 5 to 40 aromatic ring atoms, does not contain any electron-deficient heteroaryl groups and may be substituted by one or more R.sup.3 radicals; at the same time, it is possible for two or more adjacent R.sup.3 substituents together to form a mono- or polycyclic aliphatic ring system; Ar.sup.1 is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5-30 aromatic ring atoms and may be substituted by one or more nonaromatic R.sup.3 radicals; at the same time, two Ar.sup.1 radicals bonded to the same nitrogen atom, phosphorus atom or boron atom may also be bridged to one another by a single bond or a bridge selected from N(R.sup.3), C(R.sup.3).sub.2, O and S; R.sup.3 is the same or different at each instance and is selected from the group consisting of H, D, F, CN, an aliphatic hydrocarbyl radical having 1 to 20 carbon atoms and an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms in which one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN, where two or more adjacent R.sup.3 substituents together may form a mono- or polycyclic, aliphatic ring system; p is the same or different at each instance and is 0, 1, 2, 3 or 4; q is 0, 1 or 2.

2. The compound as claimed in claim 1, wherein X is the same or different at each instance and is CR.sup.1 or N, where not more than one X group per cycle is N, or in that two adjacent X groups are a group of the formula (4), where Z is the same or different at each instance and is CR.sup.1 and V is the same or different at each instance and is NR.sup.1, C(R.sup.1).sub.2, O or S, and the rest of the X groups in the cycle are CR.sup.1.

3. The compound as claimed in claim 1, wherein the compound is selected from the compounds of the formula (15) ##STR00314##

4. The compound as claimed in claim 1, wherein the compound is selected from the compounds of the formula (15a) ##STR00315##

5. The compound as claimed in claim 1, wherein R is the same or different at each instance and is selected from the group consisting of H, F, CN, N(Ar.sup.1).sub.2, a straight-chain alkyl group having 1 to 10 carbon atoms and a branched or cyclic alkyl group having 3 to 10 carbon atoms and an aromatic ring system which has 6 to 30 aromatic ring atoms and may be substituted by one or more nonaromatic R.sup.3 radicals.

6. The compound as claimed in claim 1, wherein the compound is selected from the compounds of the formula (15b) ##STR00316##

7. The compound as claimed in claim 1, wherein the compounds of formula (3) contains a total of at least 12 aromatic ring atoms in the Ar, R.sup.1 and R.sup.2 substituents.

8. The compound as claimed in claim 1, wherein Ar is selected from the groups of the formulae Ar-1 to Ar-58 ##STR00317## ##STR00318## ##STR00319## ##STR00320## ##STR00321## ##STR00322## ##STR00323## ##STR00324## ##STR00325## ##STR00326## ##STR00327## where R* has the definitions given in claim 1, the dotted bond represents the bond to the group of the formula (3) and, in addition: Ar.sup.2 is the same or different at each instance and is a bivalent aromatic or heteroaromatic ring system which has 6 to 18 aromatic ring atoms, does not contain any electron-deficient heteroaryl groups and may be substituted in each case by one or more R.sup.2 radicals; Ar.sup.3 is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 6 to 18 aromatic ring atoms, does not contain any electron-deficient heteroaryl groups and may be substituted in each case by one or more R.sup.2 radicals; Y is the same or different at each instance and is C(R.sup.2).sub.2, NR.sup.2, O or S; n is 0 or 1, where n=0 means that no Y group is bonded at this position and R.sup.2 radicals thereof are bonded to the corresponding carbon atoms instead; where the Ar-1 to Ar-57 groups can also bind via a bridging group to the nitrogen atom in formula (3).

9. The compound as claimed in claim 1, wherein R.sup.1 is the same or different at each instance and is selected from the group consisting of H, D, N(Ar.sup.1).sub.2, a straight-chain alkyl group having 1 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms, each of which may be substituted by one or more R.sup.3 radicals, where one or more hydrogen atoms may be replaced by D or F, or an aromatic or heteroaromatic ring system which has 5 to 30 aromatic ring atoms and may be substituted in each case by one or more R.sup.3 radicals.

10. The compound as claimed in claim 1, wherein R.sup.1, when it is an aromatic or heteroaromatic ring system, is selected from the groups R.sup.1-1 to R.sup.1-43 ##STR00328## ##STR00329## ##STR00330## ##STR00331## ##STR00332## ##STR00333## where R.sup.3 has the definitions given in claim 1, the dotted bond represents the bond to the group of the formula (3) and, in addition: A is the same or different at each instance and is CR.sup.3 or N, where not more than 3 X symbols per cycle are N; Y is the same or different at each instance and is C(R.sup.3).sub.2, NR.sup.3, O or S; Ar.sup.2, Ar.sup.3 is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 18 aromatic ring atoms, each of which may be substituted in each case by one or more R.sup.3 radicals; n is 0 or 1, where n=0 means that no Y group is bonded at this position and R.sup.3 radicals thereof are bonded to the corresponding carbon atoms instead; where the R.sup.1-1 to R.sup.1-42 groups can also bind via a bridging group to the nitrogen atom in formula (3).

11. An oligomer, polymer or dendrimer containing one or more compounds as claimed in claim 1, wherein one or more bonds of the compound to the polymer, oligomer or dendrimer are present in place of substituents at one or more positions.

12. A formulation comprising at least one compound as claimed in claim 1 and at least one further compound.

13. A formulation comprising at least one oligomer, polymer or dendrimer as claimed in claim 11 and at least one solvent.

14. An electronic device comprising the compound as claimed in claim 1.

15. An electronic device comprising the oligomer, polymer or dendrimer as claimed in claim 11.

16. The electronic device as claimed in claim 14, 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, dye-sensitized organic solar cells, organic optical detectors, organic photoreceptors, organic field-quench devices, light-emitting electrochemical cells, organic laser diodes and organic plasmon-emitting devices.

17. An organic electroluminescent device which comprises the compound as claimed in claim 1 is used as matrix material for phosphorescent or fluorescent emitters and/or in an electron-blocking or exciton-blocking layer and/or in a hole transport layer and/or in a hole blocker layer and/or in a hole blocker or electron transport layer.

18. A formulation comprising at least one compound as claimed in claim 1 and at least a solvent.

Description

EXAMPLES

(1) The syntheses which follow, unless stated otherwise, are conducted under a protective gas atmosphere in dried solvents. The solvents and reagents can be purchased from ALDRICH or ABCR. The numbers given for the reactants that are not commercially available are the corresponding CAS numbers.

Synthesis Examples

Example 1a: 1-(2-Chlorophenylamino)fluoren-9-one

(2) ##STR00141##

(3) In a 1 L four-neck flask, 52 g (166 mmol) of 1-iodofluoren-9-one (CAS 52086-21-2), 19.0 mL (171 mmol) of 2-chloroaniline (CAS 95-51-2), 59.8 g (432 mmol) of potassium carbonate, 3.85 g (6.6 mmol) of XantPhos and 746 mg (3.3 mmol) of palladium diacetate were dissolved in 390 mL of toluene and heated under reflux for 13 h until conversion was complete. After cooling to room temperature, the organic phase is extended with 200 mL of toluene and hydrolyzed with 500 mL of water. The organic phase is washed once with 300 mL of water and twice with 200 mL each time of 3M HCl solution. The organic phase is filtered through Al.sub.2O.sub.3. After the removal of the solvents under reduced pressure, the product is obtained as an orange solid. The yield is 48.0 g (157 mmol, corresponding to 95%).

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

(5) TABLE-US-00002 Reactant 1 Reactant 2 Product Yield 1b   7285-66-7 83% 1c   858426-71-8 78% 1d   133617-97-7 0 67% 1e   76838-82-9 53% 1f   42265-67-8 73% 1g   57013-94-2 68% 1h 0   from Ex. 7q   95/−51 70% 1i   from Ex. 7p   95-51-2 72%

Example 2a: 11H-11-Azaindeno[2,1-a]fluoren-12-one

(6) ##STR00166##

(7) A 500 mL four-neck flask is initially charged with 24 g (78 mmol) of 1a, 28.2 g (204 mmol) of potassium carbonate, 35 mg (1.5 mmol) of palladium diacetate, 1.2 g (3.0 mmol) of tricyclohexylphosphine tetrafluoroborate in 250 mL of DMAc, and the mixture is stirred at 145° C. for three days. On completion of conversion, the mixture is cooled down to room temperature and hydrolyzed with 200 mL of water. The precipitated solid is filtered and washed with water (2×300 mL). After extraction by stirring twice with ethanol at 60° C., the product is obtained as an ochre solid. The yield is 18.3 g (68 mmol, corresponding to 87% of theory).

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

(9) TABLE-US-00003 Reactant Product Yield 2b 72% 2c 0 73% 2d 67% 2e 56% 2f 71% 2g 67% 2h 0 65% 2i 68%

Example 3a: 11-Biphenyl-4-yl-11H-11-azaindeno[2,1-a]fluoren-12-one

(10) ##STR00183##

(11) A 1 L four-neck flask is initially charged with 16 g (59 mmol) of 2a, 29.6 mL (119 mmol) of 4-bromobiphenyl and 30.5 g of NaOtBu (32 mmol) in p-xylene. To this suspension are added 0.33 g (1.5 mmol) of Pd(OAc).sub.2 and 2.9 mL of a 1 M tri-tert-butylphosphine solution in toluene. The reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is removed, washed three times with 200 mL each time of water and then concentrated to dryness. The residue is subjected to hot extraction with toluene and recrystallized from toluene. The yield is 22.3 g (53 mmol, corresponding to 90%).

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

(13) TABLE-US-00004 Reactant 1 Reactant 2 Product Yield 3b   [36809-26-4] 83%  3c   [499128-71-1] 83%  3d 0   [57102-42-8] 82%  3e   [63524-03-8] 77%  3f   [94994-62-4] 90%  3g 00   [36809-26-4] 01 78%  3h 02 03   [89827-45-2] 04 88%  3i 05 06 07 83%  3j 08 09 0 84%  3k   28320-31-2 81%  3l   92-66-0 86%  3m 78%  3n 0 76%  3o 91%  3p 21%* 3q 0 38%* *Further purification by means of recrystallization from toluene/heptane and zone sublimation (340° C., 10.sup.−5 bar) up to an HPLC purity of >99.9%.

Example 4a: Bromination

(14) ##STR00232##

(15) In a 1000 mL four-neck flask, 19.5 g (72.5 mmol) of 11H-11-azaindeno[2,1-a]fluoren-12-one and 13.5 g (75 mmol) of NBS are dissolved in 700 mL of THF and stirred at room temperature for 48 h until conversion is complete. This is followed by hydrolysis with 50 mL of water and removal of the organic solvents under reduced pressure. The solid obtained is extracted once by stirring with 300 mL of hot ethanol. After cooling to room temperature, the solids are filtered off. After drying under reduced pressure, the product is obtained as a colorless solid. The yield is 22.6 g (65 mmol, corresponding to 90% of theory).

Example 5a: Borylation

(16) ##STR00233##

(17) In a 2 L four-neck flask, 24.7 g (71 mmol) of 8-bromo-11H-11-azaindeno[2,1-a]fluoren-12-one, 21.9 g (86 mmol) of bispinacolatodiborane (73183-34-3), 21.7 g (221 mmol) of potassium acetate and 1.7 g (2.1 mmol) of 1,1-bis(diphenylphosphino)ferrocenedichloropalladium(II) complex with DCM were heated under reflux in 1000 mL of anhydrous dioxane for 16 h until conversion was complete. After cooling down to room temperature, the organic phase is extended with ethyl acetate, washed three times with 300 mL of water and dried over sodium sulfate. The combined organic phases are concentrated to dryness by rotary evaporation. After recrystallization from heptane, the product is obtained in solid form. The yield is 21.3 g (54 mmol; 61%).

Example 6a

(18) ##STR00234##

(19) 12.6 g (32 mmol) of 8-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-1H-11-azaindeno[2,1-a]fluoren-12-one, 10.3 g (32 mmol) of 3-bromo-9-phenyl-9H-carbazole [1153-85-1] and 31 ml (63 mmol) of Na.sub.2CO.sub.3 (2 M solution) are suspended in 120 mL of toluene and 120 mL of ethanol. 0.73 g (0.63 mmol) of Pd(PPh.sub.3).sub.4 is added to this suspension, and the reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is removed, filtered through silica gel, washed three times with 200 mL of water and then concentrated to dryness. The residue is recrystallized from toluene. The yield is 14.8 g (29 mmol), corresponding to 91% of theory.

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

(21) TABLE-US-00005 Reactant 1 Reactant 2 Product Yield 6b   [36809-26-4] 83% 6c   [499128-71-1] 0 83% 6d   [57102-42-8] 82% 6e   [63524-03-8] 77% 6f   [94994-62-4] 90% 6g 0   [89827-45-2] 78%

Example 7a: 12′-Biphenyl-4-ylspiro[9H-fluoren-9,11(12H)-indeno[2,1a]carbazole]

(22) ##STR00253##

(23) A 1 L four-neck flask is initially charged with 23 g (99 mol) of 2-bromobiphenyl in 100 mL of THF and cooled to −78° C. By means of a dropping funnel, 41.0 mL (103 mmol) of n-butyllithium (2.5 M in n-hexane) are added dropwise at this temperature and the mixture is stirred for 1 h. Subsequently, 20.6 g (49 mmol) of 11-biphenyl-4-yl-11H-11-azaindeno[2,1-a]fluoren-12-one, dissolved in 300 mL of THF, are added by means of a dropping funnel and the mixture is warmed to room temperature within 3 h. This is followed by hydrolysis with 500 mL of water and removal of the organic solvents on a rotary evaporator. The solid that precipitates out is filtered, suspended in 400 mL of glacial acetic acid and, after addition of 150 mL of concentrated hydrochloric acid, stirred at 100° C. for 2 h. After cooling to room temperature, hydrolysis is effected with 400 mL of water, and the precipitated solids are filtered off and washed with 200 mL of water, ethanol (200 mL) and finally with 200 mL of n-heptane. The solids are subjected to hot extraction and recrystallization with n-heptane/toluene over alumina. 20.1 g (42.0 mmol, corresponding to 85%) of the product are obtained as a white solid. Further purification is effected by means of recrystallization from toluene/heptane and zone sublimation (265° C., 10.sup.−5 bar). The yield is 8.4 g (15 mmol, corresponding to 32%, HPLC purity >99.9%).

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

(25) TABLE-US-00006 Reactant 1 Reactant 2 Product Yield 7b   2052-07-5 31% 7c   2052-07-5 27% 7d 0   2052-07-5 36% 7e   2052-07-5 35% 7f   2052-07-5 38% 7g 0   2052-07-5 39% 7h   2052-07-5 36% 7i   2052-07-5 33% 7j   2052-07-5 0 35% 7k   2052-07-5 27% 7l   2052-07-5 29% 7m   2052-07-5 36% 7n 0   2052-07-5 37% 7o comp.   2052-07-5 38% 7p   13029-09-9 64% (without sublimation) 7g 00   13029-09-9 01 65% (without sublimation)

Production of the OLEDs

(26) In examples C1 to I16 which follow (see tables 1 and 2), the data of various OLEDs are presented.

Pretreatment for Examples C1-I16

(27) Glass plates coated with structured ITO (indium tin oxide) of thickness 50 nm, for improved processing, 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 Deutschland, spun on from aqueous solution). These coated glass plates form the substrates to which the OLEDs are applied.

(28) The OLEDs basically have the following layer structure: substrate/hole transport layer (HTL)/optional interlayer (IL)/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. The exact structure of the OLEDs can be found in Table 1. A reference such as “7a” means the compound of example 7a. The further materials used for production of the OLEDs are shown in Table 3.

(29) All 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 IC1:IC3:TEG1 (55%:35%:10%) mean here that the material IC1 is present in the layer in a proportion by volume of 55%, IC3 in a proportion of 35% and TEG1 in a proportion of 10%. Analogously, the electron transport layer may also consist of a mixture of two materials.

(30) The OLEDs are characterized in a standard manner. For this purpose, the electroluminescence spectra, the current efficiency (measured in cd/A), the power efficiency (measured in Im/W) and the external quantum efficiency (EQE, measured in percent) are, as a function of luminance, calculated from current-voltage-luminance characteristics (IUL characteristics) assuming Lambertian radiation characteristics. The electroluminescence spectra are determined at a luminance of 1000 cd/m.sup.2, and the CIE 1931 x and y color coordinates are calculated therefrom. The parameter U1000 in Table 2 refers to the voltage which is required for a luminance of 1000 cd/m.sup.2. CE1000 and PE1000 respectively refer to the current and power efficiencies which are achieved at 1000 cd/m.sup.2. Finally, EQE1000 refers to the external quantum efficiency at an operating luminance of 1000 cd/m.sup.2.

(31) The data for the various OLEDs are collated in Table 2. Example C1 is a comparative example according to the prior art; examples I11-I16 show data of OLEDs of the invention.

(32) Some of the examples are elucidated in detail hereinafter, in order to illustrate the advantages of the OLEDs of the invention.

Use of Mixtures of the Invention in the Emission Layer of Phosphorescent OLEDs

(33) The materials of the invention, when used as matrix materials in phosphorescent OLEDs, show improvements in power efficiency compared to the prior art. By using the compound 7a of the invention in combination with the green-emitting dopant TEG1 and the matrix ST1, it is possible to achieve a rise in power efficiency by about 15% compared to the prior art 70 (examples C1, I1).

(34) TABLE-US-00007 TABLE 1 Structure of the OLEDs HTL IL EBL EML HBL ETL EIL Ex. thickness thickness thickness thickness thickness thickness thickness C1 SpA1 HATCN SpMA1 ST1:7o:TEG1 IC1 ST2:LiQ (50%:50%) — 70 nm 5 nm 90 nm (30%:58%:12%) 30 nm 10 nm 30 nm I1 SpA1 HATCN SpMA1 ST1:7a:TEG1 IC1 ST2:LiQ (50%:50%) — 70 nm 5 nm 90 nm (30%:58%:12%) 30 nm 10 nm 30 nm I2 SpA1 HATCN SpMA1 ST1:7b:TEG1 IC1 ST2:LiQ (50%:50%) — 70 nm 5 nm 90 nm (44%:44%:12%) 30 nm 10 nm 30 nm I3 SpA1 HATCN SpMA1 ST1:7c:TEG1 IC1 ST2:LiQ (50%:50%) — 70 nm 5 nm 90 nm (58%:30%:12%) 30 nm 10 nm 30 nm I4 SpA1 HATCN SpMA1 ST1:7d:TEG1 IC1 ST2:LiQ (50%:50%) — 70 nm 5 nm 90 nm (32%:56%:12%) 30 nm 10 nm 30 nm I5 SpA1 HATCN SpMA1 IC2:7e:TER1 — ST2:LiQ (50%:50%) — 90 nm 5 nm 130 nm (30%:60%:10%) 40 nm 40 nm I6 SpA1 HATCN SpMA1 ST1:7f:TEG1 IC1 ST2:LiQ (50%:50%) — 70 nm 5 nm 90 nm (32%:56%:12%) 30 nm 10 nm 30 nm I7 SpA1 HATCN SpMA1 ST1:7g:TEG1 IC1 ST2:LiQ (50%:50%) — 70 nm 5 nm 90 nm (44%:44%:12%) 30 nm 10 nm 30 nm I8 SpA1 HATCN SpMA1 ST1:7h:TEG1 IC1 ST2:LiQ (50%:50%) — 70 nm 5 nm 90 nm (30%:58%:12%) 30 nm 10 nm 30 nm I9 SpA1 HATCN SpMA1 ST1:7i:TEG1 IC1 ST2:LiQ (50%:50%) — 70 nm 5 nm 90 nm (44%:44%:12%) 30 nm 10 nm 30 nm I10 SpA1 HATCN SpMA1 ST1:7j:TEG1 IC1 ST2:LiQ (50%:50%) — 70 nm 5 nm 90 nm (56%:32%:12%) 30 nm 10 nm 30 nm I11 SpA1 HATCN SpMA1 ST1:7k:TEG1 IC1 ST2:LiQ (50%:50%) — 70 nm 5 nm 90 nm (34%:54%:12%) 30 nm 10 nm 30 nm I12 SpA1 HATCN SpMA1 IC2:7l:TER1 — ST2:LiQ (50%:50%) — 90 nm 5 nm 130 nm (30%:60%:10%) 40 nm 40 nm I13 SpA1 HATCN SpMA1 IC2:7m:TER1 — ST2:LiQ (50%:50%) — 90 nm 5 nm 130 nm (45%:45%:10%) 40 nm 40 nm I14 SpA1 HATCN SpMA1 IC2:7n:TER1 — ST2:LiQ (50%:50%) — 90 nm 5 nm 130 nm (30%:60%:10%) 40 nm 40 nm I15 SpA1 HATCN SpMA1 ST1:3p:TEG1 IC1 ST2:LiQ (50%:50%) — 70 nm 5 nm 90 nm (32%:56%:12%) 30 nm 10 nm 30 nm I16 SpA1 HATCN SpMA1 ST1:3q:TEG1 IC1 ST2:LiQ (50%:50%) — 70 nm 5 nm 90 nm (32%:56%:12%) 30 nm 10 nm 30 nm

(35) TABLE-US-00008 TABLE 2 U1000 CE1000 PE1000 EQE CIE x/y at Ex. (V) (cd/A) (lm/W) 1000 1000 cd/m.sup.2 C1 3.4 58 54 15.6% 0.33/0.62 I1 3.2 64 62 17.2% 0.34/0.63 I2 3.4 68 63 18.4% 0.34/0.62 I3 3.3 67 64 18.1% 0.34/0.63 I4 3.1 63 64 16.9% 0.33/0.62 I5 4.3 11 8 12.1% 0.67/0.33 I6 3.3 61 58 16.5% 0.33/0.62 I7 3.5 67 60 17.9% 0.34/0.62 I8 3.4 65 60 17.6% 0.33/0.63 I9 3.6 70 61 18.7% 0.34/0.62 I10 3.4 68 63 18.2% 0.33/0.62 I11 3.2 62 61 16.6% 0.33/0.63 I12 4.1 13 10 12.4% 0.66/0.34 I13 4.2 14 10 13.3% 0.67/0.33 I14 4.3 14 10 12.8% 0.66/0.34 I15 3.4 63 58 16.8% 0.33/0.62 I16 3.5 65 58 17.5% 0.34/0.63

(36) TABLE-US-00009 TABLE 3 Structural formulae of the materials for the OLEDs 02 HATCN 03 SpA1 04 SpMA1 05 LiQ 06 ST1 07 ST2 08 IC1 09 IC2 0 TEG1 TER1