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MATERIALS FOR ORGANIC ELECTROLUMINESCENT DEVICES

20180370938 · 2018-12-27

    Inventors

    Cpc classification

    International classification

    Abstract

    The present invention relates to compounds of the formula (1) which are suitable for use in electronic devices, in particular organic electroluminescent devices, and to electronic devices which comprise these compounds.

    ##STR00001##

    Claims

    1.-18. (canceled)

    19. A compound of the formula (1), ##STR00512## where the following applies to the symbols and indices used: Ar.sup.1 is a group of formula (Ar1-1), ##STR00513## Ar.sup.2 is a group of formula (Ar2-1) or (Ar2-2), ##STR00514## V, Z, T, Q are on each occurrence, identically or differently, N or CR.sup.1, with the proviso that there is a maximum of three N atoms per 6-membered rings; or V is C and is linked to one adjacent group Z, which is also C, via a bridge E.sup.1; or V is C and is linked to one adjacent group T, which is also C, via a bridge E.sup.1; or V is C and is linked to one adjacent group Q, which is also C, via a bridge E.sup.1; or two adjacent groups V (V-V or V=V), two adjacent groups T (T-T or T=T), two adjacent groups Z (Z-Z or Z=Z) and/or two adjacent groups Q (Q-Q or Q=Q) stand for a group of the formula (E-1), ##STR00515## in which the dashed lines indicate respectively the linking to the rest of the 6-membered ring comprising the groups V, the rest of the 6-membered ring comprising the groups T, the rest of the 6-membered ring comprising the groups Z or the rest of the 6-membered ring comprising the groups Q; E.sup.1, E.sup.2 are identically or differently on each occurrence, a divalent bridge selected from B(R.sup.0), C(R.sup.0).sub.2, Si(R.sup.0).sub.2, CO, CNR.sup.0, CC(R.sup.0).sub.2, O, S, SO, SO.sub.2, N(R.sup.0), P(R.sup.0) and P(O)R.sup.0; Ar.sup.L is an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.1; R, R.sup.0, R.sup.1 are selected on each occurrence, identically or differently, from the group consisting of H, D, F, Cl, Br, I, CHO, CN, C(O)Ar.sup.3, P(O)(Ar.sup.3).sub.2, S(O)Ar.sup.3, S(O).sub.2Ar.sup.3, NO.sub.2, Si(R.sup.2).sub.3, B(OR.sup.2).sub.2, OSO.sub.2R.sup.2, straight-chain alkyl, alkoxy or thioalkyl groups having 1 to 40 C atoms or branched or cyclic alkyl, alkoxy or thioalkyl groups having 3 to 40 C atoms, each of which may be substituted by 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, Ge(R.sup.2).sub.2, Sn(R.sup.2).sub.2, CO, CS, CSe, 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, aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.2, and aryloxy groups having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R.sup.2, where two adjacent substituents R, two adjacent substituents R.sup.0 and/or two adjacent substituents R.sup.1, may form a mono- or polycyclic, aliphatic ring system or aromatic ring system, 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, CHO, CN, C(O)Ar.sup.3, P(O)(Ar.sup.3).sub.2, S(O)Ar3, S(O).sub.2Ar3, NO2, Si(R3)3, B(OR3)2, OSO2R3, straight-chain alkyl, alkoxy or thioalkyl groups having 1 to 40 C atoms or branched or cyclic alkyl, alkoxy or thioalkyl groups having 3 to 40 C atoms, each of which may be substituted by one or more radicals R.sup.3, where in each case one or more non-adjacent CH2 groups may be replaced by R.sup.3CCR.sup.3, CC, Si(R.sup.3).sub.2, Ge(R.sup.3).sub.2, Sn(R.sup.3).sub.2, CO, CS, CSe, P(O)(R.sup.3), SO, SO.sub.2, 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, aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.3, and aryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R.sup.3, where two adjacent substituents R.sup.2 may form a mono- or polycyclic, aliphatic ring system or aromatic ring system, which may be substituted by one or more radicals R.sup.3; R.sup.3 is selected on each occurrence, identically or differently, from the group consisting of H, D, F, Cl, Br, I, CN, straight-chain alkyl, alkoxy or thioalkyl groups having 1 to 20 C atoms or branched or cyclic alkyl, alkoxy or thioalkyl groups having 3 to 20 C atoms, where in each case one or more non-adjacent CH.sub.2 groups may be replaced by SO, SO.sub.2, O, S and where one or more H atoms may be replaced by D, F, Cl, Br or I, and aromatic or heteroaromatic ring system having 5 to 24 C atoms; Ar.sup.3 is an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may in each case also be substituted by one or more radicals R.sup.3; i is on each occurrence, identically or differently, 0 or 1; m, n are, identically or differently, 0 or 1; s, p, r are, identically or differently, 0, 1, 2, 3 or 4; where r+n4 and p+m4; q is 0, 1 or 2.

    20. The compound according to claim 19, wherein m+n=0.

    21. The compound according to claim 19, wherein the index i is 0.

    22. The compound according to claim 19, wherein Ar.sup.2 is selected from the groups of formulae (Ar2-3) to (Ar2-6), ##STR00516## where the symbols Z, V, T and Q have the same meaning as defined in claim 19.

    23. The compound according to claim 19, wherein the group Ar.sup.1 is selected from the groups of formula (Ar1-2), ##STR00517## where R.sup.1 has the same meaning as in claim 19 and where E.sup.3 is a divalent bridge selected from B(R.sup.0), C(R.sup.0).sub.2, Si(R.sup.0).sub.2, CO, CNR.sup.0, CC(R.sup.0).sub.2, O, S, SO, SO.sub.2, N(R.sup.0), P(R.sup.0) and P(O)R.sup.0, where R0 has the same meaning as in claim 19; t is 0 or 1; where t is 0 means that the divalent bridge E.sup.3 is absent; u is 0, 1, 2, 3 or 4; where u+t4 v is 0, 1, 2, 3, 4 or 5; where v+t5.

    24. The compound according to claim 19, wherein the group Ar.sup.2 is selected from the groups of the following formulae (Ar2-7) to (Ar2-10), ##STR00518## where the symbols E.sup.1, R.sup.1 have the same meaning as in claim 19, and where a, b, c, d are, identically or differently, 0 or 1; x, z, g are identically or differently, 0, 1, 2, 3, 4 or 5; where a+b+x5 and z+c5 in formulae (Ar2-7), a+x5 and z+c5 in formula (Ar2-8), a+b+x5 and z+c+d5 in formula (Ar2-9) and g+c+d5 in formula (Ar2-10); y is 0, 1, 2 or 3; where y+a+b+c3 in formulae (Ar2-7), y+a+c3 in formula (Ar2-8) and y+a+b+c+d3 in formula (Ar2-9); e, f are identically or differently, 0, 1, 2, 3 or 4; where e+a+b4 and f+a+b+c+d4.

    25. The compound according to claim 24, wherein a+b1 and c+d1.

    26. The compound according to claim 24, wherein c=d=0.

    27. The compound according to claim 19, wherein E.sup.1, E.sup.2 and/or E.sup.3 are, identically or differently, selected from C(R.sup.0).sub.2, O, S and N(R.sup.0).

    28. The compound according to claim 19, wherein R.sup.0 is selected on each occurrence, identically or differently, from the group consisting of H, D, F, CN, Si(R.sup.2).sub.3, straight-chain alkyl groups having 1 to 10 C atoms or branched or cyclic alkyl groups having 3 to 10 C atoms, each of which may be substituted by one or more radicals R.sup.2, where in each case one or more H atoms may be replaced by F, and aryl or heteroaryl groups having 5 to 40 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.2, where two adjacent substituents R.sup.0 may form a mono- or polycyclic, aliphatic ring system or aromatic ring system, which may be substituted by one or more radicals R.sup.2.

    29. The compound according to claim 19, wherein the group Ar.sup.2 is selected from the group of formulae (Ar2-7-1) to (Ar2-10-1), ##STR00519## where the symbol R.sup.1 has the same meaning as in claim 19, and x, z, g are 0, 1, 2, 3, 4 or 5; y is 0, 1, 2 or 3; and e, f are 0, 1, 2, 3 or 4.

    30. The compound according to claim 19, wherein Ar.sup.L is selected from aromatic or heteroaromatic ring systems having 5 to 14 aromatic ring atoms, which may in each case also be substituted by one or more radicals R.sup.2.

    31. Compound according to claim 19, wherein R, R.sup.1 are selected, identically or differently on each occurrence, from the group consisting of H, D, F, CN, straight-chain alkyl or alkoxy groups having 1 to 10 C atoms or branched or cyclic alkyl or alkoxy groups having 3 to 10 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 O and where one or more H atoms may be replaced by F, and aromatic or heteroaromatic ring systems having 5 to 24 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.2.

    32. A process for the preparation of the compound according to claim 19, which comprises introducing a diarylamino group by a CN coupling reaction between a 1- or 3- or 4-halogenated spirobifluorene and a diarylamine or triarylamine.

    33. A formulation comprising at least one compound according to claim 19 and at least one solvent.

    34. An electronic device comprising at least one compound according to claim 19.

    35. The electronic device as claimed in claim 34, 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-sensitised organic solar cells, organic optical detectors, organic photoreceptors, organic field-quench devices, light-emitting electrochemical cells, organic laser diodes and organic plasmon emitting devices.

    36. An organic electroluminescent device which comprises the compound according to claim 19 is employed as hole-transport material in a hole-transport or hole-injection or exciton-blocking or electron-blocking layer or as matrix material for fluorescent or phosphorescent emitters.

    Description

    EXAMPLES

    A) Synthesis Examples

    [0149] The following syntheses are carried out under a protective-gas atmosphere, unless indicated otherwise. The starting materials can be purchased from ALDRICH or ABCR. The numbers in square brackets in the case of the starting materials known from the literature are the corresponding CAS numbers.

    Example 1

    Synthesis of biphenyl-4-yl-([1,1;3,1]terphenyl-4-yl-9,9-spirobifluoren-4-yl)amine (1-1) and derivatives (1-2) to (1-25)

    [0150] ##STR00322##

    a) Synthesis of intermediate biphenyl-4-yl-[1,1;3,1]terphenyl-4-yl-amine (I-1)

    [0151] 1,1-Bis(diphenylphosphino)ferrocene (0.9 g, 1.67 mmol), palladium acetate (360 mg, 1.67 mmol) and sodium tert-butoxide (10.1 g, 105 mmol) are added to a solution of biphenyl-4-ylamine (13.7 g, 80.8 mmol) and 4-Bromo-[1,1;3,1 ]terphenyl (25 g, 80.8 mmol) in degassed toluene (400 ml), and the mixture is heated under reflux for 20 h. The reaction mixture is cooled to room temperature, diluted with toluene and filtered through Celite. The filtrate is diluted with water, re-extracted with toluene, and the combined organic phases are dried and evaporated in vacuo. The residue is filtered through silica gel (heptane/dichloromethane) and crystallised from isopropanol. Biphenyl-4-yl-[1,1;3,1 ]terphenyl-4-yl-amine is obtained in the form of a pale-yellow solid (27 g, 85% of theory).

    b) Synthesis of biphenyl-4-yl-([1,1;3,1 ]terphenyl-4-yl-9,9-spirobifluoren-4-yl)amine (1-1)

    [0152] Tri-tert-butylphosphine (2.5 ml of a 1.0 M solution in toluene, 2.5 mmol), palladium acetate (284 mg, 1.26 mmol) and sodium tert-butoxide (9.12 g, 95 mmol) are added to a solution of biphenyl-4-yl-[1,1;3,1 ]terphenyl-4-yl-amine (25.2 g, 63 mmol) and 4-bromo-9,9-spirobifluorene (25 g, 63 mmol) in degassed toluene (500 ml), and the mixture is heated under reflux for 3 h. The reaction mixture is cooled to room temperature, diluted with toluene and filtered through Celite. The filtrate is evaporated in vacuo, and the residue is crystallised from toluene/heptane. The crude product is extracted in a Soxhlet extractor (toluene) and purified by recrystallization in heptane/toluene (23 g, 51% of theory). After sublimation in vacuo, the product is isolated in the form of an off-white solid.

    [0153] The following compounds are obtained analogously:

    TABLE-US-00003 Aryl- Aryl- Ex. Arylamine bromide 1 bromide 2 Product Yield 1-1 [00323]embedded image [92-67-1] [00324]embedded image [60631-86-3] [00325]embedded image [1161009-88-6] [00326]embedded image 43% 1-2 [00327]embedded image [108714-73-4] [00328]embedded image [60631-86-3] [00329]embedded image [1161009-88-6] [00330]embedded image 38% 1-3 [00331]embedded image [108714-73-4] [00332]embedded image [1762-84-1] [00333]embedded image [1161009-88-6] [00334]embedded image 63% 1-4 [00335]embedded image [4106-66-5] [00336]embedded image [1762-84-1] [00337]embedded image [1161009-88-6] [00338]embedded image 48% 1-5 [00339]embedded image [25288-76-0] [00340]embedded image [1762-84-1] [00341]embedded image [1161009-88-6] [00342]embedded image 52% 1-6 [00343]embedded image [108714-73-4] [00344]embedded image [103068-20-8] [00345]embedded image [1161009-88-6] [00346]embedded image 39% 1-7 [00347]embedded image [4106-66-5] [00348]embedded image [103068-20-8] [00349]embedded image [1161009-88-6] [00350]embedded image 45% 1-8 [00351]embedded image [25288-76-0] [00352]embedded image [103068-20-8] [00353]embedded image [1161009-88-6] [00354]embedded image 51% 1-9 [00355]embedded image [92-67-1] [00356]embedded image [103068-20-8] [00357]embedded image [1161009-88-6] [00358]embedded image 60% 1-10 [00359]embedded image [108714-73-4] [00360]embedded image [1047992-04-0] [00361]embedded image [1161009-88-6] [00362]embedded image 45% 1-11 [00363]embedded image [92-67-1] [00364]embedded image [1047992-04-0] [00365]embedded image [1161009-88-6] [00366]embedded image 45% 1-12 [00367]embedded image [108714-73-4] [00368]embedded image [574750-94-0] [00369]embedded image [1161009-88-6] [00370]embedded image 51% 1-13 [00371]embedded image [4106-66-5] [00372]embedded image [1047992-04-0] [00373]embedded image [1161009-88-6] [00374]embedded image 52% 1-14 [00375]embedded image [92-67-1] [00376]embedded image [1047992-04-0] [00377]embedded image [1361227-58-8] [00378]embedded image 55% 1-15 [00379]embedded image [108714-73-4] [00380]embedded image [1186644-60-9] [00381]embedded image [1361227-58-8] [00382]embedded image 29% 1-16 [00383]embedded image [92-67-1] [00384]embedded image [00385]embedded image [1161009-88-6] [00386]embedded image 34% 1-17 [00387]embedded image [92-67-1] [00388]embedded image [1021857-42-0] [00389]embedded image [1161009-88-6] [00390]embedded image 48% 1-18 [00391]embedded image [4106-66-5 [00392]embedded image [00393]embedded image [1161009-88-6] [00394]embedded image 26% 1-19 [00395]embedded image [92-67-1] [00396]embedded image [00397]embedded image [1161009-88-6] [00398]embedded image 33% 1-20 [00399]embedded image [108714-73-4] [00400]embedded image [1047992-04-0] [00401]embedded image [1361227-58-8] [00402]embedded image 35% 1-21 [00403]embedded image [108714-73-4] [00404]embedded image [60631-86-3] [00405]embedded image [1361227-58-8] [00406]embedded image 42% 1-22 [00407]embedded image [108714-73-4] [00408]embedded image [103068-20-8] [00409]embedded image [1361227-58-8] [00410]embedded image 47% 1-23 [00411]embedded image [92-67-1] [00412]embedded image [1205547-68-7] [00413]embedded image [1361227-58-8] [00414]embedded image 39% 1-24 [00415]embedded image [108714-73-4] [00416]embedded image [1047992-04-0] [00417]embedded image [1450933-18-2] [00418]embedded image 27% 1-25 [00419]embedded image [25288-76-0] [00420]embedded image [1047992-04-0] [00421]embedded image [1450933-18-2] [00422]embedded image 30% 1-26 [00423]embedded image [108714-73-4] [00424]embedded image [24253-40-5] [00425]embedded image [1161009-88-6] [00426]embedded image 36%

    Example 2

    Synthesis of (9,9-dimethyl-9H-fluoren-2-yl)-[1,1;3,1 ]terphenyl-4-yl-[4-(9,9-spiro-bifluoren-4-yl)-phenyl]-amine (2-1) and the derivatives (2-2) to (2-4)

    [0154] ##STR00427##

    a) Synthesis of 4-chloro-4-[(9,9-spiro-bifluoren)]. Intermediate 11-1

    [0155] 49 g (320 mmol) of 4-chloro-phenylboronic acid, 120 g (304 mmol) of 4-bromo-spirobifluorene, 3.51 g (3.04 mmol) of Pd(PPh.sub.3).sub.4, 122 g (1 mol) of potassium carbonate are dissolved in 700 mL of toluene. The reaction mixture is refluxed and stirred under an argon atmosphere for 12 hours and after cooling to room temperature, the mixture is filtered through Celite. The filtrate is evaporated in vacuo, and the residue is crystallised from heptane. The product is isolated in the form of a white solid (110 g, 85% of theory).

    b) (9,9-dimethyl-9H-fluoren-2-yl)-[1,1;3,1 ]terphenyl-4-yl-[4-(9,9-spiro-bifluoren-4-yl)-phenyl]-amine (2-1)

    [0156] The synthesis of intermediates III and compounds 2-1 to 2-4 are carried out analogously as described for the synthesis of intermediate I-1 and compound 1-1.

    TABLE-US-00004 Aryl- Aryl- Ex. Arylamine bromide 1 bromide 2 Product Yield 2-1 [00428]embedded image [00429]embedded image [00430]embedded image [00431]embedded image 35% [108714-73-4] [60631-86-3] [1427189-08-3] 2-2 [00432]embedded image [00433]embedded image [00434]embedded image [00435]embedded image 20% [108714-73-4] [103068-20-8] 2-3 [00436]embedded image [00437]embedded image [00438]embedded image [00439]embedded image 28% [92-67-1] [60631-86-3] 2-4 [00440]embedded image [00441]embedded image [00442]embedded image [00443]embedded image 40% [4106-66-5 [103068-20-8]

    [0157] Comparative Examples ST1 to ST8 are Obtained Analogously:

    TABLE-US-00005 Aryl- Aryl- Ex. Arylamine bromide 1 bromide 2 Product ST-1 [00444]embedded image [00445]embedded image [00446]embedded image [00447]embedded image ST-2 [00448]embedded image [00449]embedded image [00450]embedded image [00451]embedded image ST-3 [00452]embedded image [00453]embedded image [00454]embedded image [00455]embedded image ST-4 [00456]embedded image [00457]embedded image [00458]embedded image [00459]embedded image ST-5 [00460]embedded image [00461]embedded image [00462]embedded image [00463]embedded image ST-6 [00464]embedded image [00465]embedded image [00466]embedded image [00467]embedded image ST-7 [00468]embedded image [00469]embedded image [00470]embedded image [00471]embedded image ST-8 [00472]embedded image [00473]embedded image [00474]embedded image [00475]embedded image

    B) Devices Examples

    [0158] 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).

    [0159] The data for various OLEDs are presented in Examples below (see Tables 1 to 2). The substrates used are glass plates coated with structured ITO (indium tin oxide) in a thickness of 50 nm. The OLEDs basically have the following layer structure: substrate/hole-injection layer (HIL)/hole-transport layer (HTL)/electron-blocking layer (EBL)/emission layer (EML)/electron-transport layer (ETL)/electron-injection layer (EIL) and finally a cathode. The cathode is formed by an aluminium layer 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.

    [0160] 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 matrix materials in a certain proportion by volume by coevaporation. An expression such as H1:SEB (5%) here means that material H1 is present in the layer in a proportion by volume of 95% and SEB is present in the layer in a proportion of 5%. Analogously, other layers may also consist of a mixture of two or more materials. The OLEDs are characterised by standard methods. For this purpose, the electroluminescence spectra and the external quantum efficiency (EQE, given 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 expression EQE @ 10 mA/cm.sup.2 denotes the external quantum efficiency at an operating current density of 10 mA/cm.sup.2. LT80 @60 mA/cm.sup.2 is the lifetime until the OLED has dropped from its initial luminance of i.e. 5000 cd/m.sup.2 to 80% of the initial intensity, i.e. to 4000 cd/m.sup.2 without using any acceleration factor. The data for the various OLEDs containing inventive and comparative materials are summarised in table 2.

    Use of Compounds According to the Invention as Hole-Transport Materials in Fluorescent OLEDs

    [0161] In particular, compounds according to the invention are suitable as HIL, HTL, EBL or matrix material in the EML in OLEDs. They are suitable as a single layer, but also as mixed component as HIL, HTL, EBL or within the EML. Compared with components from prior art (V1 to V9), the samples comprising the compounds according to the invention exhibit higher efficiencies and/or improved lifetimes both in singlet blue and also in triplet green.

    TABLE-US-00006 TABLE 1 Structure of the OLEDs HIL HTL EBL EIL Thickness/ Thickness/ Thickness/ EML ETL Thickness/ Ex. nm nm nm Thickness/nm Thickness/nm nm V1 HIM: HIM HTMV1 H1:SEB(5%) ETM:LiQ(50%) LiQ F4TCNQ(5%) 180 nm 10 nm 20 nm 30 nm 1 nm 20 nm V2 HIM: HIM HTMV2 H1:SEB(5%) ETM:LiQ(50%) LiQ F4TCNQ(5%) 180 nm 10 nm 20 nm 30 nm 1 nm 20 nm V3 HIM: HIM HTMV3 H1:SEB(5%) ETM:LiQ(50%) LiQ F4TCNQ(5%) 180 nm 10 nm 20 nm 30 nm 1 nm 20 nm V4 HIM: HIM HTMV4 H1:SEB(5%) ETM:LiQ(50%) LiQ F4TCNQ(5%) 180 nm 10 nm 20 nm 30 nm 1 nm 20 nm V5 HIM: HIM HTMV5 H1:SEB(5%) ETM:LiQ(50%) LiQ F4TCNQ(5%) 180 nm 10 nm 20 nm 30 nm 1 nm 20 nm V6 HIM: HIM HTMV6 H1:SEB(5%) ETM:LiQ(50%) LiQ F4TCNQ(5%) 180 nm 10 nm 20 nm 30 nm 1 nm 20 nm V7 HIM: HIM HTMV7 H1:SEB(5%) ETM:LiQ(50%) LiQ F4TCNQ(5%) 180 nm 10 nm 20 nm 30 nm 1 nm 20 nm V8 HIM: HIM HTMV8 H1:SEB(5%) ETM:LiQ(50%) LiQ F4TCNQ(5%) 180 nm 10 nm 20 nm 30 nm 1 nm 20 nm V9 HIM: HIM HTMV9 H1:SEB(5%) ETM:LiQ(50%) LiQ F4TCNQ(5%) 180 nm 10 nm 20 nm 30 nm 1 nm 20 nm E1 HIM: HIM HTM1 H1:SEB(5%) ETM:LiQ(50%) LiQ F4TCNQ(5%) 180 nm 10 nm 20 nm 30 nm 1 nm 20 nm E2 HIM: HIM HTM2 H1:SEB(5%) ETM:LiQ(50%) LiQ F4TCNQ(5%) 180 nm 10 nm 20 nm 30 nm 1 nm 20 nm E3 HIM: HIM HTM3 H1:SEB(5%) ETM:LiQ(50%) LiQ F4TCNQ(5%) 180 nm 10 nm 20 nm 30 nm 1 nm 20 nm E4 HIM: HIM HTM4 H1:SEB(5%) ETM:LiQ(50%) LiQ F4TCNQ(5%) 180 nm 10 nm 20 nm 30 nm 1 nm 20 nm E5 HIM: HIM HTM5 H1:SEB(5%) ETM:LiQ(50%) LiQ F4TCNQ(5%) 180 nm 10 nm 20 nm 30 nm 1 nm 20 nm E6 HIM: HIM HTM6 H1:SEB(5%) ETM:LiQ(50%) LiQ F4TCNQ(5%) 180 nm 10 nm 20 nm 30 nm 1 nm 20 nm E7 HIM: HIM HTM7 H1:SEB(5%) ETM:LiQ(50%) LiQ F4TCNQ(5%) 180 nm 10 nm 20 nm 30 nm 1 nm 20 nm E8 HIM: HIM HTM8 H1:SEB(5%) ETM:LiQ(50%) LiQ F4TCNQ(5%) 180 nm 10 nm 20 nm 30 nm 1 nm 20 nm E9 HIM: HIM HTM9 H1:SEB(5%) ETM:LiQ(50%) LiQ F4TCNQ(5%) 180 nm 10 nm 20 nm 30 nm 1 nm 20 nm E10 HIM: HIM HTM10 H1:SEB(5%) ETM:LiQ(50%) LiQ F4TCNQ(5%) 180 nm 10 nm 20 nm 30 nm 1 nm 20 nm E11 HIM: HIM HTM11 H1:SEB(5%) ETM:LiQ(50%) LiQ F4TCNQ(5%) 180 nm 10 nm 20 nm 30 nm 1 nm 20 nm E12 HIM: HIM HTM12 H1:SEB(5%) ETM:LiQ(50%) LiQ F4TCNQ(5%) 180 nm 10 nm 20 nm 30 nm 1 nm 20 nm E13 HIM: HIM HTM13 H1:SEB(5%) ETM:LiQ(50%) LiQ F4TCNQ(5%) 180 nm 10 nm 20 nm 30 nm 1 nm 20 nm E14 HIM: HIM HTM14 H1:SEB(5%) ETM:LiQ(50%) LiQ F4TCNQ(5%) 180 nm 10 nm 20 nm 30 nm 1 nm 20 nm E15 HIM: HIM HTM15 H1:SEB(5%) ETM:LiQ(50%) LiQ F4TCNQ(5%) 180 nm 10 nm 20 nm 30 nm 1 nm 20 nm E16 HIM: HIM HTM16 H1:SEB(5%) ETM:LiQ(50%) LiQ F4TCNQ(5%) 180 nm 10 nm 20 nm 30 nm 1 nm 20 nm E17 HIM: HIM HTM17 H1:SEB(5%) ETM:LiQ(50%) LiQ F4TCNQ(5%) 180 nm 10 nm 20 nm 30 nm 1 nm 20 nm E18 HIM: HIM HTM18 H1:SEB(5%) ETM:LiQ(50%) LiQ F4TCNQ(5%) 180 nm 10 nm 20 nm 30 nm 1 nm 20 nm E19 HIM: HIM HTM19 H1:SEB(5%) ETM:LiQ(50%) LiQ F4TCNQ(5%) 180 nm 10 nm 20 nm 30 nm 1 nm 20 nm E20 HIM: HIM HTM20 H1:SEB(5%) ETM:LiQ(50%) LiQ F4TCNQ(5%) 180 nm 10 nm 20 nm 30 nm 1 nm 20 nm E21 HIM: HIM HTM21 H1:SEB(5%) ETM:LiQ(50%) LiQ F4TCNQ(5%) 180 nm 10 nm 20 nm 30 nm 1 nm 20 nm

    TABLE-US-00007 TABLE 2 Data for the OLEDs U EQE LT80 @ 10 mA/cm.sup.2 @ 10 mA/cm.sup.2 @ 60 mA/cm.sup.2 Ex. [V] % [h] HTMV1 3.8 7.6 210 HTMV2 3.7 7.9 120 HTMV3 3.7 7.5 90 HTMV4 4.2 9.3 170 HTMV5 4.0 9.0 110 HTMV6 3.7 6.9 240 HTMV7 4.1 8.5 55 HTMV8 4.1 9.3 250 HTMV9 3.9 7.6 215 HTM1 3.9 7.5 220 HTM2 3.8 7.7 125 HTM3 3.8 7.4 90 HTM4 3.7 7.9 155 HTM5 3.6 7.5 150 HTM6 3.6 7.2 115 HTM7 3.8 8.0 300 HTM8 3.7 7.8 135 HTM9 3.9 7.4 165 HTM10 3.9 8.0 180 HTM11 3.9 8.4 185 HTM12 4.2 8.1 285 HTM13 4.0 8.6 195 HTM14 4.1 8.4 160 HTM15 4.0 8.6 85 HTM16 3.9 8.7 120 HTM17 4.0 8.4 125 HTM18 4.0 9.1 115 HTM19 4.0 9.0 265 HTM20 4.0 8.9 275 HTM21 4.1 8.7 285

    TABLE-US-00008 TABLE 3 Structures of the materials used [00476]embedded image F4TCNQ [00477]embedded image HIM [00478]embedded image H1 [00479]embedded image SEB [00480]embedded image ETM [00481]embedded image LiQ [00482]embedded image HTMV1 [00483]embedded image HTMV2 [00484]embedded image HTMV3 [00485]embedded image HTMV4 [00486]embedded image HTMV5 [00487]embedded image HTMV6 [00488]embedded image HTMV7 [00489]embedded image HTMV8 [00490]embedded image HTMV9 [00491]embedded image HTM1 [00492]embedded image HTM2 [00493]embedded image HTM3 [00494]embedded image HTM4 [00495]embedded image HTM5 [00496]embedded image HTM6 [00497]embedded image HTM7 [00498]embedded image HTM8 [00499]embedded image HTM9 [00500]embedded image HTM10 [00501]embedded image HTM11 [00502]embedded image HTM12 [00503]embedded image HTM13 [00504]embedded image HTM14 [00505]embedded image HTM15 [00506]embedded image HTM16 [00507]embedded image HTM17 [00508]embedded image HTM18 [00509]embedded image HTM19 [00510]embedded image HTM20 [00511]embedded image HTM21

    Examples

    [0162] OLED devices with the structures shown in table 1 are produced. Table 2 shows the performance data of the examples described. The device is a fluorescent blue device with comparison of HTMV1 and HTM1 as material in the electron blocking layer (EBL). It can be shown, that the lifetime of device E1 is better than the comparative example V1. Material HTM4 shows lower voltage and higher efficiency in device (E4) than comparative example V1. Materials HTM10 and HTM11 show at least higher efficiencies in devices (E10, E11) than comparative example V1. Material HTM12 shows better efficiency and better lifetime in device (E12) than comparative example V1.

    [0163] Compared to reference material HTMV2 the inventive materials HTM2, HTM8 and HTM9 show better lifetime (V2 vs. E2, E8, E9). Material HTM15 shows better efficiency than reference material HTMV2 (E15 vs. V2). Material HTM5 has lower voltage and better efficiency than HTMV2 (E5 vs. V2). Material HTM14 have better efficiency and better lifetime in device (E14) than reference device V2.

    [0164] Compared to reference Material HTMV3 and reference device V3 the inventive material HTM3 has higher lifetime in device E3, material HTM15 shows much higher efficiency in device 15 and material HTM6 has lower voltage and higher lifetime in device E6. Material HTM11 shows better lifetime compared to reference material HTMV4 (E11 vs. V4). Compared to reference material HTMV6 the inventive material HTM1 has better efficiency (E1 vs. E6).

    [0165] Compared to reference material HTMV5 the device (E16) with material HTM16 has lower voltage and better lifetime than reference (V5). Material HTM17 shows better lifetime than reference (V5 vs. E17). Material HTM18 shows better efficiency and lifetime compared to reference device (E18 vs. V5).

    [0166] Compared to reference material HTMV7 the inventive material HTM13 shows lower voltage, better efficiency and better lifetime (V7 vs. E13). Compared to reference material HTMV8 the inventive materials HTM19, HTM20 and HTM21 have similar or better voltage and better lifetimes (V8 vs. E19, E20 and E21).

    [0167] Compared to reference material HTMV9 the material HTM7 shows better voltage, better efficiency and better lifetime.