Materials for organic electroluminescent devices

Abstract

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

Claims

1. A compound of formula (1) ##STR00800## where the symbols and indices used are as follows: X is the same or different at each instance and is CR or N, where X=C when a Y.sup.1 or Y.sup.2 group is bonded to this X; Ar together with the carbon atoms explicitly shown is an aryl or heteroaryl group which has 5 to 14 aromatic ring atoms and may be substituted by one or more R radicals; Y.sup.1 is C(R′)2, NR′, O, S, C═O, Si(R′)2, BR′, PR′, P(═O)R′, SO or SO.sub.2; Y.sup.2 is a single bond, C(R′).sub.2, C(═C(R″).sub.2), NR′, O, S, C′O, Si(R′).sub.2, BR′, PR′, P(═O)R′, SO or SO.sub.2; R is the same or different at each instance and is H, D, F, Cl, Br, I, N(R.sup.1).sub.2, N(Ar′).sub.2, CN, NO.sub.2, OR.sup.1, SR.sup.1, COOR.sup.1, 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 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 group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group may in each case be substituted by one or more R.sup.1 radicals and where one or more nonadjacent CH.sub.2 groups is optionally replaced by Si(R.sup.1).sub.2, C═O, NR.sup.1, O, S or CONR.sup.1, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms, and or is optionally substituted in each case by one or more R.sup.1 radicals; at the same time, two R radicals together optionally form an aliphatic or heteroaliphatic ring system; R′ is the same or different at each instance and is a straight-chain alkyl 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 group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group may in each case be substituted by one or more R.sup.1 radicals and where one or more nonadjacent CH.sub.2 groups may be replaced by Si(R.sup.1).sub.2, C═O, NR.sup.1, O, S or CONR.sup.1, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms, and may be substituted in each case by one or more R.sup.1 radicals; at the same time, two R′ radicals together may also form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system; R″ is the same or different at each instance and is one of the following: (a)R, one R″ is R and the other R″ is CR.sup.1═CR.sup.1 or CR.sup.1═N or (c) R” together with Ar, forms an aromatic or heteroaromatic ring system; Ar′ is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.1 radicals; R.sup.1 is the same or different at each instance and is H, D, F, Cl, Br, I, N(R.sup.2).sub.2, CN, NO.sub.2, OR.sup.2, SR.sup.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 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 group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group may in each case be substituted by one or more R.sup.2 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by Si(R.sup.2).sub.2, C═O, NR.sup.2, O, S or CONR.sup.2, or 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.2 radicals; at the same time, two or more R.sup.1 radicals together may form a ring system; R.sup.2 is the same or different at each instance and is H, D, F or an aliphatic, aromatic or heteroaromatic organic radical having 1 to 20 carbon atoms, in which one or more hydrogen atoms may also be replaced by F; M and n are independently 0 or 1, with the proviso that m+n=1 or 2; m=0 means that the Y.sup.1 is absent and an R radical is bonded to the carbon atom in Ar to which Y.sup.1 would be bonded; in addition, n=0 means that the Y.sup.2 group is absent and an R radical is bonded to the carbon atom in Ar to which Y.sup.2 would be bonded; where the following compounds are excluded from the invention: ##STR00801##

2. The compound as claimed in claim 1, wherein the compound of the formula (I) is of the formula (2a), (2b), (2c), (2d), (2e), (2f), (2g) or (2h) ##STR00802## ##STR00803## where the symbols used have the definitions given in claim 1.

3. The compound as claimed in claim 1, wherein Ar is selected from the groups of formulae (Ar-a), (Ar-b) and (Ar-c) ##STR00804## where one of the dotted bonds represents the bond to the nitrogen atom and the other dotted bond represents the bond to Y.sup.1 or Y.sup.2 and X has the definitions given in claim 1.

4. The compound as claimed in claim 1, wherein the compound of the formula (I) is a compound of formula (3) ##STR00805## where the symbols and indices used have the definitions given in claim 1 and where, when m=0 or n=0, and R radical is bonded at the position to which Y.sup.1 or Y.sup.2 would be bonded.

5. The compound as claimed in claim 1, wherein the compound is selected from the compounds of the formulae (4a) to (4h) ##STR00806## ##STR00807## where the symbols used have the definitions given in claim 1.

6. The compound as claimed in claim 1, wherein the compound is selected from the compounds of the formulae (5a) to (5k) ##STR00808## ##STR00809## ##STR00810## where the symbols used have the definitions given in claim 1.

7. The compound as claimed in claim 1, wherein the compound is selected from the compounds of the formulae (6a) to (6u) ##STR00811## ##STR00812## ##STR00813## ##STR00814## ##STR00815## where the symbols used have the definitions given in claim 1.

8. The compound as claimed in claim 1, wherein the compound is selected from the compounds of the formulae (7a) to (7h) ##STR00816## ##STR00817## where the symbols used have the definitions given in claim 1.

9. 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, D, F, N(Ar′).sub.2, CN, OR.sup.1, a straight-chain alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms, where the alkyl or alkenyl group may in each case be substituted by one or more R.sup.1 radicals, and where one or more nonadjacent CH.sub.2 groups may be replaced by O, or an aromatic or heteroaromatic ring system which has 6 to 30 aromatic ring atoms and may be substituted in each case by one or more R.sup.1 radicals; at the same time, two R radicals together may also form an aliphatic ring system.

10. The compound as claimed in claim 1, wherein R′ bonded to N, B or P is an aromatic or heteroaromatic ring system which has 6 to 30 aromatic ring atoms and may be substituted by one or more R.sup.1 radicals, and in that R′ bonded to C or Si is the same or different at each instance and is selected from the group consisting of a straight-chain alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms, where the alkyl or alkenyl group may in each case be substituted by one or more R.sup.1 radicals, and where one or more nonadjacent CH.sub.2 groups may be replaced by O, or an aromatic or heteroaromatic ring system which has 6 to 30 aromatic ring atoms and may be substituted in each case by one or more R.sup.1 radicals; at the same time, two R′ radicals together may also form aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system.

11. The compound as claimed in claim 1, wherein the compound contains (1) at least one substituent R which is (a) an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms and is optionally substituted by one or more R.sup.1 radicals, or (b) N(Ar′).sub.2, (2) at least one Y.sup.1 or Y.sup.2 group which is NR′ where R′ from an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.1 radicals.

12. A formulation comprising the compound as claimed in claim 1 and at least one solvent and/or at least one further organic or inorganic compound.

13. An electronic device comprising at least one compound as claimed in claim 1.

14. The electronic device as claimed in claim 13, wherein the device is an organic electroluminescent device.

15. An organic electroluminescent device which comprises the compound as claimed in claim 1 in an emitting layer as matrix material for phosphorescent or fluorescent emitters or for emitters that exhibit TADF, or in an electron transport layer and/or in a hole transport layer and/or in an exciton blocker layer and/or in a hole blocker layer.

16. The compound as claimed in claim 1, wherein R.sup.2 is the same or different at each instance and is H, D, F or a hydrocarbyl radical having 1 to 20 carbon atoms, in which one or more hydrogen atoms may also be replaced by F.

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.

a) 1-Chloro-7-(9-phenyl-9H-carbazol-3-yl)-10H-phenothiazine

(2) ##STR00307##

(3) 20.9 g (67 mmol) of 7-bromo-1-chloro-10H-phenothiazine, 17 g (664 mmol) of 2-N-phenylcarbazole-3-boronic acid and 13.7 g (100 mmol) of sodium tetraborate are dissolved in 100 ml of THF and 60 ml of water and degassed. 0.9 g (1.3 mmol) of bis(triphenylphosphine)palladium(II) chloride and 1 g (20 mmol) of hydrazinium hydroxide are added. The reaction mixture is then stirred under a protective gas atmosphere at 70° C. for 48 h. The cooled solution is supplemented with toluene, washed repeatedly with water, dried and concentrated. The product is purified via column chromatography on silica gel with toluene/heptane (1:2). Yield: 19.8 g (40 mmol), 62% of theory.

(4) The following compounds are prepared in an analogous manner:

(5) TABLE-US-00003 Reactant 1 Reactant 2 Product Yield  1a 08 09 0 34%  2a 36%  3a 48%  4a 46%  5a 0 47%  6a 44%  7a 38%  8a 0  9a 36% 10a 53% 11a 0 42% 12a 51% 13a 50% 14a 63% 15a 0 52% 16a 56% 17a 50% 18a 0 47% 19a 42% 20a 40%

b) 10-(8-Bromonaphth-1-yl)-10H-phenoxazine

(6) ##STR00368##

(7) Under protective gas, 16.1 g (88 mmol) of 10H-phenoxazine, 29 g (88 mmol) of 1-bromo-8-iodobenzene and 0.8 g (0.88 mmol) of tris(dibenzylideneacetone)dipalladium were suspended in 500 ml of toluene. The reaction mixture is heated under reflux for 8 h. After cooling, the organic phase is removed, washed three times with 200 ml of water and then concentrated to dryness. The product is purified via column chromatography on silica gel with toluene/heptane (2:2). The purity is 98.0%. Yield: 26 g (67 mmol), 77% of theory.

(8) The following compounds are prepared in an analogous manner:

(9) TABLE-US-00004 Reactant 1 Reactant 2 Product Yield  2b 0 66%  3b 69%  4b 62%  5b 0 64%  6b 71%  7b 73%  8b 67%  9b 0 71% 10b 70% 11b 74% 12b 00 01 79% 13b 02 03 04 70% 15b 05 06 07 79% 16b 08 09 0 73% 17b 68% 18b 71% 19b 70% 20b 0 72% 21b 70% 22b 74% 23b 0 75% 24b 77% 25b 79% 26b 0 75% 27b 70% 28b 74% 29b 71% 30b 0 64% 31b 70% 32b 73% 33b 0 64% 34b 58% 35b 767%  36b 0 72% 37b 61% 38b 66% 39b 70% 40b 0 72% 41b 71% 42b 64% 43b 0 58% 44b 59% 45b 63% 46b 00 64% 47b 01 02 03 60% 48b 04 05 06 76% 49b 07 08 09 73% 50b 0 70% 51b 71% 52b 65% 53b 0 64% 54b 53% 55b 65%

c) 5-(8-Bromonaphth-1-yl)-5,10-dihydrophenazine

(10) ##STR00528##

(11) Under protective gas, 15.8 g (87.8 mmol) of 9,10-dihydrophenazine, 20 g (87 mmol) of 1-bromo-8-iodonaphthalene and 0.8 g (0.88 mmol) of tris(dibenzylideneacetone)dipalladium were suspended in 500 ml of toluene. The reaction mixture is heated under reflux for 8 h. After cooling, the organic phase is removed, washed three times with 200 ml of water and then concentrated to dryness. The product is purified via column chromatography on silica gel with toluene/heptane (2:2). The purity is 94.0%. Yield: 21 g (56 mmol), 65% of theory.

(12) The following compounds are prepared in an analogous manner:

(13) TABLE-US-00005 Ex. Reactant 1 Reactant 2 Product Yield 1c 0 60% 2c 62% 3c 67% 4c 0 60% 5c 65% 6c 67%

d) 5-(8-Bromonaphth-1-yl)-10-(4,6-diphenyl-[1,3,5]triazin-2-yl)-5,10-dihydrophenazine

(14) ##STR00547##

(15) 11.22 g (29 mmol) of 5-(8-bromonaphth-1-yl)-5,10-dihydrophenazine are dissolved in 225 ml of dimethylformamide under a protective gas atmosphere, and 1.5 g (37.5 mmol) of NaH, 60% in mineral oil, are added. After 1 h at room temperature, a solution of 2-chloro-4,6-diphenyl-[1,3,5]-triazine (8.5 g, 31.75 mmol) in 75 ml of dimethylformamide is added dropwise. The reaction mixture is stirred at room temperature for 12 h, then poured onto ice and extracted three times with dichloromethane. The combined organic phases are dried over Na.sub.2SO.sub.4 and concentrated. The residue is subjected to hot extraction with toluene. Yield: 14.3 g (23 mmol), 80% of theory.

(16) The following compounds are prepared in an analogous manner:

(17) TABLE-US-00006 Reactant 1 Reactant 2 Product Yield 1d 0 82% 2d 83% 3d 81% 4d 86% 5d 0 80% 6d 84% 7d 86% 8d 0 80%

e) Cyclization

(18) ##STR00572##

(19) Under protective gas, 58 g (150 mmol) of 10-(8-bromonaphth-1-yl)-10H-phenoxazine are dissolved in 500 ml of dimethylacetamide. To this solution are added 2.4 g (6.5 mmol) of tricyclohexyl tetrafluoroborate and 701 mg (3.1 mmol) of Pd(OAc).sub.2. Subsequently, the mixture is stirred at 120° C. for 9 h, then cooled to room temperature and extracted with dichloromethane. The combined organic phases are dried over Na.sub.2SO.sub.4 and concentrated. The residue is subjected to hot extraction with toluene, recrystallized from toluene and finally sublimed under high vacuum. The yield is 33 g (107 mmol), 72% of theory.

(20) The following compounds are prepared in an analogous manner:

(21) TABLE-US-00007 Reactant 1 Product Yield  2e 81%  3e 78%  4e 78%  5e 0 75%  6e 81%  7e 79%  8e 76%  9e 74% 10e 0 75% 11e 71% 12e 72% 13e 70% 14e 62% 15e 00 63% 16e 01 02 73% 17e 03 04 76% 18e 05 06 77% 19e 07 08 71% 20e 09 0 73% 21e 69% 22e 72% 23e 56% 24e 63% 25e 0 80% 26e 84% 27e 73% 28e 73% 29e 76% 30e 0 70% 31e 78% 32e 73% 33e 65% 34e 64% 35e 0 73% 36e 76% 37e 79% 38e 70% 39e 76% 40e 0 67% 41e 71% 42e 63% 43e 60% 44e 80% 45e 0 80% 46e 78% 47e 80% 48e 82% 49e 78% 50e 0 79% 51e 76% 52e 81% 53e 79% 54e 75% 55e 0 72% 56e 74% 57e 70% 58e 42% 59e 67% 60e 0 65% 61e 67%

f) 2-[2-(7-Azabenzo[de]anthracen-7-yl)phenyl]propan-2-ol

(22) ##STR00693##

(23) 73 g (211 mmol) of methyl 2-(7-azabenzo[de]anthracen-7-yl)benzoate are dissolved in 1500 ml of dried THF and degassed. The mixture is cooled to −78° C., and 569 ml (853 mmol) of methyllithium are added within 40 min. The mixture is allowed to warm up to −40° C. within 1 h, and the conversion is monitored via TLC. On completion of conversion, the mixture is quenched cautiously with MeOH at −30° C. The reaction solution is concentrated to one third of its volume 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 concentrated. The yield is 63 g (180 mmol), 87% of theory.

(24) The following compound is prepared in an analogous manner:

(25) TABLE-US-00008 Reactant 1 Product Yield 1f 80%

g) Cyclization

(26) ##STR00696##

(27) 15.5 g (43.6 mmol) of 2-[2-(7-azabenzo[de]anthracen-7-yl)phenyl]propan-2-ol are dissolved in 1200 ml of degassed toluene, a suspension of 40 g of polyphosphoric acid and 28 ml of methanesulfonic acid is added and the mixture is heated to 60° C. for 1 h. The mixture is cooled down and admixed with water. A solid precipitates out and is dissolved in CH.sub.2Cl.sub.2/THF (1:1). The solution is cautiously alkalized with 20% NaOH, and the phases are separated and dried over MgSO.sub.4. The mixture of A and B is separated by chromatography. The yield is 11.6 g (34 mmol), 64% of theory, A 31%, B 33%.

(28) The following compound is prepared in an analogous manner:

(29) TABLE-US-00009 Reactant 1 Product 1 Product 2 Yield 1g 28%: 29%

h) Bromination

(30) ##STR00700##

(31) 12.2 g (41 mmol) of product e are dissolved in 300 ml of chloroform. To this solution are added, in portions at 50° C. in the dark, 7 g (42 mmol) of NBS, and then the mixture is stirred for 1 h. After the solvent has been removed under reduced pressure, the residue is extracted by stirring in heptane/toluene 3:1 and filtered off while hot. Yield: 12.5 g (32 mmol), 81% of theory.

(32) The following compounds are prepared in an analogous manner:

(33) TABLE-US-00010 Reactant 1 Product Yield  2h 01 02 83%  3h 03 04 81%  4h 05 06 78%  5h 07 08 69%  6h 09 0 52%  7h 43%  8h 39%  9h 67% 10h 65% 11h 0 72% 12h 61% 13h 77% 14h 68%

j) Suzuki Coupling

(34) ##STR00727##

(35) Under protective gas, 62 g (150 mmol) of B-[9-(4-phenyl-2-quinazolinyl)-9H-carbazol-3-yl]boronic acid, 55 g (145 mmol) of product h and 36 g (340 mmol) of sodium carbonate are suspended in 1000 ml of ethylene glycol dimethyl ether and 280 ml of water. 1.8 g (1.5 mmol) of tetrakis(triphenylphosphine)palladium(0) are 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 product is purified via column chromatography on silica gel with toluene/heptane (1:2) and finally sublimed under high vacuum (p=5×10.sup.−7 mbar) (99.9% purity). The yield is 75 g (111 mmol), 60% of theory.

(36) The following compounds are prepared in an analogous manner:

(37) TABLE-US-00011 Reactant 1 Reactant 2  1j  3j 0  4j  5j  6j  7j  8j 0  9j 10j 11j 12j 13j 0 14j 15j 16j 17j 18j 0 19j 20j Product Yield  1j 74%  3j 81%  4j 78%  5j 79%  6j 0 75%  7j 81%  8j 78%  9j 75% 10j 70% 11j 73% 12j 72% 13j 76% 14j 73% 15j 78% 16j 0 81% 17j 76% 18j 75% 19j 70% 20j 76%
Production of the OLEDs

(38) Examples I1 to I15 which follow (see Table 1) present the use of the materials of the invention in OLEDs.

(39) Pretreatment for Examples I1-I15:

(40) Glass plaques coated with structured ITO (indium tin oxide) of thickness 50 nm are treated prior to coating, first with an oxygen plasma, followed by an argon plasma. These plasma-treated glass plaques form the substrates to which the OLEDs are applied.

(41) The OLEDs basically have the following layer structure: substrate/hole injection layer (HIL)/hole transport layer (HTL)/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.

(42) The exact structure of the OLEDs can be found in Table 1. The materials required for production of the OLEDs are shown in Table 2.

(43) 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:IV1:TER1 (50%:45%:5%) mean here that the material IC1 is present in the layer in a proportion by volume of 50%, IV1 in a proportion of 45% and TER1 in a proportion of 5%. Analogously, the electron transport layer may also consist of a mixture of two materials.

(44) The OLEDs are characterized in a standard manner. 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.

(45) Use of Mixtures of the Invention in OLEDs

(46) The materials of the invention can be used in the emission layer in phosphorescent red OLEDs. The inventive compounds IV1 to IV7 are used in Examples I1 to I15 as matrix material in the emission layer. The color coordinates of the electroluminescence spectra of the OLEDs are CIEx=0.67 and CIEy=0.33. The materials are thus suitable for use in the emission layer of red OLEDs.

(47) In addition, the materials of the invention can be used successfully in the hole blocker layer (HBL) or electron blocker layer (EBL). This is shown in examples I5 and I8 or I2, I10, I13 and I15. Here too, the color coordinates of the spectrum of each of the OLEDs are CIEx=0.67 and CIEy=0.33.

(48) TABLE-US-00012 TABLE 1 Structure of the OLEDs HIL HTL EBL EML HBL ETL Ex. thickness thickness thickness thickness thickness thickness I1 HATCN SpMA1 SpMA2 IC1:IV1:TER1 — ST1:LiQ (50%:50%) 5 nm 125 nm 10 nm (50%:45%:5%) 35 nm 40 nm I2 HATCN SpMA1 IV1 IC1:IV1:TER1 — ST1:LiQ (50%:50%) 5 nm 125 nm 10 nm (50%:45%:5%) 35 nm 40 nm I3 HATCN SpMA1 SpMA2 IV2:TER1 — ST1:LiQ (50%:50%) 5 nm 125 nm 10 nm (95%:5%) 40 nm 35 nm I4 HATCN SpMA1 SpMA2 IC2:IV2:TER1 — ST1:LiQ (50%:50%) 5 nm 125 nm 10 nm (50%:45%:5%) 35 nm 40 nm I5 HATCN SpMA1 SpMA2 IV2:TER1 IV2 ST1:LiQ (50%:50%) 5 nm 125 nm 10 nm (95%:5%) 40 nm 5 nm 35 nm I6 HATCN SpMA1 SpMA2 IV3:TER1 — ST1:LiQ (50%:50%) 5 nm 125 nm 10 nm (95%:5%) 40 nm 35 nm I7 HATCN SpMA1 SpMA2 IC2:IV3:TER1 — ST1:LiQ (50%:50%) 5 nm 125 nm 10 nm (50%:45%:5%) 35 nm 40 nm I8 HATCN SpMA1 SpMA2 IV3:TER1 IV3 ST1:LiQ (50%:50%) 5 nm 125 nm 10 nm (95%:5%) 40 nm 5 nm 35 nm I9 HATCN SpMA1 SpMA2 IC1:IV4:TER1 — ST1:LiQ (50%:50%) 5 nm 125 nm 10 nm (50%:45%:5%) 35 nm 40 nm I10 HATCN SpMA1 IV4 IC1:IV4:TER1 — ST1:LiQ (50%:50%) 5 nm 125 nm 10 nm (50%:45%:5%) 35 nm 40 nm I11 HATCN SpMA1 SpMA2 IV5:TER1 — ST1:LiQ (50%:50%) 5 nm 125 nm 10 nm (95%:5%) 40 nm 35 nm I12 HATCN SpMA1 SpMA2 IC1:IV5:TER1 — ST1:LiQ (50%:50%) 5 nm 125 nm 10 nm (50%:45%:5%) 35 nm 40 nm I13 HATCN SpMA1 IV1 IC1:IV6:TER1 — ST1:LiQ (50%:50%) 5 nm 125 nm 10 nm (50%:45%:5%) 35 nm 40 nm I14 HATCN SpMA1 SpMA2 IC1:IV7:TER1 — ST1:LiQ (50%:50%) 5 nm 125 nm 10 nm (50%:45%:5%) 35 nm 40 nm I15 HATCN SpMA1 IV1 IC1:IV7:TER1 — ST1:LiQ (50%:50%) 5 nm 125 nm 10 nm (50%:45%:5%) 35 nm 40 nm

(49) TABLE-US-00013 TABLE 2 Structural formulae of the materials for the OLEDs HATCN SpMA1 SpMA2 ST1 TER1 0 LiQ IC1 IC2 IV1 IV2 IV3 IV4 IV5 IV6 IV7