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MATERIALS FOR ELECTRONIC DEVICES

20230225196 · 2023-07-13

    Inventors

    Cpc classification

    International classification

    Abstract

    The present application relates to materials for use in electronic devices, to processes for preparing the materials, and to electronic devices containing the materials.

    Claims

    1.-19. (canceled)

    20. Compound of formula (1) ##STR00777## where the symbols used are as follows: X is O or S; Y is the same or different at each instance and is CR.sup.7 or N; L is a divalent aromatic ring system having 6 to 40 aromatic ring atoms; R.sup.1, R.sup.4, R.sup.6 and R.sup.7 are the same or different at each instance and are selected from H, D, F, Cl, Br, I, C(═O)R.sup.11, CN, Si(R.sup.11).sub.3, N(R.sup.11).sub.2, P(═O)(R.sup.11).sub.2, OR.sup.11, S(═O)R.sup.11, S(═O).sub.2R.sup.11, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R.sup.1 radicals may be joined to one another and may form a ring and/or two or more R.sup.4 radicals may be joined to one another and may form a ring and/or two or more R.sup.6 radicals may be joined to one another and may form a ring and/or two or more R.sup.7 radicals may be joined to one another and may form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned may each be substituted by R.sup.11 radicals; and where one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups may be replaced by —R.sup.11C═CR.sup.11—, —C≡C—, Si(R.sup.11).sub.2, C═O, C═NR.sup.11, —C(═O)O—, —C(═O)NR.sup.11—, NR.sup.11, P(═O)(R.sup.11), —O—, —S—, SO or SO.sub.2; R.sup.2 and R.sup.3 are the same or different at each instance and are selected from straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where the two R.sup.2 and R.sup.3 radicals may be joined to one another and may form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned may each be substituted by R.sup.11 radicals; and where one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups may be replaced by —R.sup.11C═CR.sup.11—, —C≡C—, Si(R.sup.11).sub.2, C═O, C═NR.sup.11, —C(═O)O—, —C(═O)NR.sup.11—, NR.sup.11, P(═O)(R.sup.11), —O—, —S—, SO or SO.sub.2; if the two R.sup.2 and R.sup.3 radicals form a ring, the result is a spiro compound; R.sup.5 is an aromatic ring system which has 6 to 40 aromatic ring atoms and may be substituted by one or more R.sup.11 radicals, or a heteroaromatic ring system which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.11 radicals; R.sup.11 is the same or different at each instance and is selected from H, D, F, Cl, Br, I, C(═O)R.sup.12, CN, Si(R.sup.12).sub.3, N(R.sup.12).sub.2, P(═O)(R.sup.2).sub.2, OR.sup.12, S(═O)R.sup.12, S(═O).sub.2R.sup.12, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R.sup.11 radicals may be joined to one another and may form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned are each substituted by R.sup.12 radicals; and where one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by —R.sup.12C═CR.sup.12—, —C≡C—, Si(R.sup.12).sub.2, C═O, C═NR.sup.12, —C(═O)O—, —C(═O)NR.sup.12—, NR.sup.12, P(═O)(R.sup.2), —O—, —S—, SO or SO.sub.2; where two or more R.sup.11 radicals may not form a ring with one another; R.sup.12 is the same or different at each instance and is selected from H, D, F, Cl, Br, I, CN, alkyl or alkoxy groups having 1 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where the alkyl, alkoxy, alkenyl and alkynyl groups, aromatic ring systems and heteroaromatic ring systems mentioned may be substituted by one or more radicals selected from F and CN; m is 0, 1, 2, 3 or 4; n is 0, 1, 2 or 3; o is 0, 1, 2 or 3.

    21. Compound according to claim 20, characterized in that L is selected from the following formulae: ##STR00778## where: R.sup.8 is the same or different at each instance and is selected from H, D, F, Cl, Br, I, C(═O)R.sup.11, CN, Si(R.sup.11).sub.3, N(R.sup.11).sub.2, P(═O)(R.sup.11).sub.2, OR.sup.11, S(═O)R.sup.11, S(═O).sub.2R.sup.11, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more Re radicals may be joined to one another and may form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned may each be substituted by R.sup.11 radicals; and where one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by —R.sup.11C═CR.sup.11—, —C≡C—, Si(R.sup.11).sub.2, C═O, C═NR.sup.11, —C(═O)O—, —C(═O)NR.sup.11—, NR.sup.11, P(═O)(R.sup.11), —O—, —S—, SO or SO.sub.2; p is 0, 1, 2, 3 or 4; q is 0, 1, 2, 3, 4, 5 or 6; r is 0, 1, 2, 3, 4, 5, 7, 8, 9, 10, 11 or 12; s is 0, 1, 2, 3, 4, 5, 7 or 8; t is 0, 1, 2, 3, 4, 5, 7, 8, 9 or 10.

    22. Compound according to claim 20, characterized in that L is selected from the following formulae: ##STR00779##

    23. Compound according to claim 20, characterized in that L is selected from the following formulae: ##STR00780## ##STR00781##

    24. Compound according to claim 20, characterized in that L is selected from the following formulae: ##STR00782## ##STR00783## ##STR00784##

    25. Compound according to claim 20, characterized in that L is selected from the following formulae: ##STR00785##

    26. Compound according to claim 20, characterized in that the compound is selected from the following formulae: ##STR00786## ##STR00787##

    27. Compound according to claim 20, characterized in that it is a monoamine compound.

    28. Compound according to claim 20, characterized in that R.sup.2 and R.sup.3 are the same or different at each instance and are selected from straight-chain alkyl groups having 1 to 10 carbon atoms, branched or cyclic alkyl groups having 3 to 10 carbon atoms or aromatic ring systems having 6 to 18 aromatic atoms; where the two R.sup.2 and R.sup.3 radicals may be joined to one another and may form a ring; where the alkyl groups mentioned and the aromatic ring systems mentioned may each be substituted by R.sup.11 radicals; if the two R.sup.2 and R.sup.3 radicals form a ring, the result is a spiro compound, preferably a spirobifluorene.

    29. Compound according to claim 20, characterized in that the R.sup.5 radicals are selected from the following formulae: ##STR00788## ##STR00789## ##STR00790## ##STR00791## ##STR00792## ##STR00793## ##STR00794## ##STR00795## ##STR00796## ##STR00797## ##STR00798## ##STR00799## ##STR00800## ##STR00801## ##STR00802## ##STR00803## ##STR00804## ##STR00805## ##STR00806## ##STR00807## ##STR00808## ##STR00809## ##STR00810## ##STR00811## ##STR00812## ##STR00813## ##STR00814## ##STR00815## ##STR00816## ##STR00817## ##STR00818## ##STR00819## ##STR00820## ##STR00821## ##STR00822## ##STR00823## ##STR00824## ##STR00825## ##STR00826## ##STR00827## ##STR00828## ##STR00829## ##STR00830## ##STR00831## ##STR00832## where the R.sup.5 radicals mentioned may be substituted by R.sup.11 radicals at the positions shown as unsubstituted, and where the dotted bond is the bond to the amine nitrogen atom.

    30. Compound according to claim 20, characterized in that m, n and o are 0.

    31. Process for preparing a compound according to claim 20 with the aid of Suzuki coupling or the Buchwald reaction.

    32. Oligomer, polymer or dendrimer containing one or more compounds according to claim 20, wherein the bond(s) to the polymer, oligomer or dendrimer may be localized at any desired positions substituted by R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.11 or R.sup.12 in formula (1).

    33. Composition comprising one or more compounds of the formula (1) and at least one further material selected from the group consisting of the hole transport materials, hole injection materials, p-dopants, electron blocker materials, matrix materials, emitters and electron transport materials.

    34. Formulation comprising at least one compound according to claim 20, and at least one solvent.

    35. Electronic device comprising at least one compound according to claim 20.

    36. Electronic device according to claim 35, characterized in that it is an organic electroluminescent device and comprises anode, cathode and at least one emitting layer, and in that the compound is present in an electron-blocking layer or in a hole-transporting layer or in an emitting layer of the device.

    37. Organic electroluminescent device according to claim 36, characterized in that the compound is present in a hole-transporting layer which is a hole transport layer or an electron blocker layer.

    38. Use of a compound according to claim 20 in an electronic device.

    Description

    EXAMPLES

    A) Synthesis Examples

    [0160] Quite generally, the compounds of the invention are synthesized by methods that are very well known to the person skilled in the art in the field. First of all, the fluorene is converted by means of Suzuki coupling. In a second step, the product from the first reaction is converted to the ultimate product by means of a Buchwald reaction.

    a).SUB.3.-(4-Chlorophenyl)-9,9-dimethyl-9H-fluorene

    [0161] ##STR00688##

    [0162] 39.5 g (166 mmol, 1.10 eq) of (9,9-dimethyl-9H-fluoren-3-yl)boronic acid [CAS 1251773-34-8], 30.6 g (160 mmol, 1.00 eq) of 1-bromo-4-chlorobenzene [CAS 106-39-8] and 102 g (480 mmol; 3.00 eq) of potassium phosphate [CAS 7778-53-2] are dissolved in 2000 ml of toluene [CAS 108-88-3] and 200 ml of water. After inertization in an argon stream for 45 minutes, 3.70 g (3.20 mmol, 2.00 mol %) of tetrakis(triphenylphosphine)palladium is added and the mixture is heated to reflux for 16 hours. After cooling to room temperature, the organic phase is removed and the aqueous phase is extracted with ethyl acetate. The combined organic phases are washed with water and dried over Na.sub.2SO.sub.4. After the solvent has been removed under reduced pressure, the solids obtained are taken up in methylene chloride and precipitated by addition of ethanol. After this operation has been performed repeatedly, 40.5 g (133 mmol, 83% of theory) of the product is obtained.

    [0163] The following are obtained analogously:

    TABLE-US-00006 No. Reactant 1 Reactant 2 Product Yield 1a [00689]embedded image [00690]embedded image [00691]embedded image 80% [CAS 1251773-34-8] [CAS 108-37-2] 2a [00692]embedded image [00693]embedded image [00694]embedded image 68% [CAS 1635401-03-4] [CAS 2413379-08-3] 3a [00695]embedded image [00696]embedded image [00697]embedded image 72% [CAS 1319162-39-4] [CAS 23055-77-8] 4a [00698]embedded image [00699]embedded image [00700]embedded image 55% [CAS 1319162-42-9] [CAS 108-37-2] 5a [00701]embedded image [00702]embedded image [00703]embedded image 61% [CAS 1319162-39-4] [CAS 53220-82-9] 6a [00704]embedded image [00705]embedded image [00706]embedded image 64% [CAS 1635401-03-4] [CAS 77332-65-1] 7a [00707]embedded image [00708]embedded image [00709]embedded image 70% [CAS 1251773-34-8] [CAS 915031-07-1] 8a [00710]embedded image [00711]embedded image [00712]embedded image 79% [CAS 1635401-03-4] [CAS 164334-69-4] 9a [00713]embedded image [00714]embedded image [00715]embedded image 69% [CAS 1251773-34-8] [CAS 2403429-47-8] 10a [00716]embedded image [00717]embedded image [00718]embedded image 71% [CAS 1251773-34-8] [CAS 844856-42-4]

    b) N-[4-(9,9-dimethyl-9H-fluoren-3-yl)phenyl]-N-(4-{8-oxatricyclo[7.4.0.02,7]trideca1(9),2(7),3,5,10,12-hexaen-6-yl}phenyl)-[1,1′-biphenyl]-4-amine

    [0164] ##STR00719##

    [0165] An initial charge of 40.0 g (131 mmol; 1.00 eq.) of 3-(4-chlorophenyl)-9,9-dimethyl-9H-fluorene, 54.0 g (131 mmol; 1.00 eq.) of N-(4-{8-oxatricyclo[7.4.0.0.sup.2,7]trideca-1(9),2(7),3,5,10,12-hexaen-6-yl}phenyl)-[1,1′-biphenyl]-4-amine [CAS 955959-89-4] and 15.9 g (144 mmol; 1.10 eq.) of sodium tert-pentoxide [CAS 14593-46-5] in 2000 ml of toluene [CAS 108-88-3] is inertized in an argon stream for 30 minutes. Thereafter, 1.62 mg (3.94 mmol; 3 mol %) of dicyclohexyl-(2′,6′-dimethoxybiphenyl-2-yl)phosphine (SPhos) [CAS 657408-07-6] and 886 mg (3.94 mmol; 3 mol %) of palladium acetate [CAS 3375-31-3] are added and the mixture is heated to reflux for 18 hours. After completion of conversion and cooling to room temperature, water is added to the reaction. After separation of the phases and extraction of the aqueous phase with toluene [CAS 108-88-3], the combined organic phases are concentrated and heptane is added. The precipitated solids are isolated. Purification by means of Soxhlet extraction, recrystallization and vacuum sublimation gives the desired product (52.0 g; 77.1 mmol; 59% of theory).

    [0166] The following are obtained analogously:

    TABLE-US-00007 No Reactant 1 Reactant 2 Product Yield 1b [00720]embedded image [00721]embedded image [00722]embedded image 56% [CAS 955959-89-4] 2b [00723]embedded image [00724]embedded image [00725]embedded image 62% [CAS 2097371-73-6] 3b [00726]embedded image [00727]embedded image [00728]embedded image 48% [CAS 2376742-43-5] 4b [00729]embedded image [00730]embedded image [00731]embedded image 42% [CAS 2378356-50-2] 5b [00732]embedded image [00733]embedded image [00734]embedded image 55% [CAS 2244106-56-5] 6b [00735]embedded image [00736]embedded image [00737]embedded image 58% [CAS 2173402-40-7] 7b [00738]embedded image [00739]embedded image [00740]embedded image 63% [CAS 2097371-73-6] 8b [00741]embedded image [00742]embedded image [00743]embedded image 51% [CAS 1381976-37-9] 9b [00744]embedded image [00745]embedded image [00746]embedded image 57% [CAS 1381976-37-9] 10 b [00747]embedded image [00748]embedded image [00749]embedded image 45% [CAS 955959-89-4] 11 b [00750]embedded image [00751]embedded image [00752]embedded image 60% [CAS 2097371-73-6] 13 b [00753]embedded image [00754]embedded image [00755]embedded image 55% [CAS 1547491-60-0] 14 b [00756]embedded image [00757]embedded image [00758]embedded image 52% [CAS 1922919-50-3] 15 b [00759]embedded image [00760]embedded image [00761]embedded image 63% [CAS 2244106-56-5] 16 b [00762]embedded image [00763]embedded image [00764]embedded image 60% [CAS 2244205-92-1]

    [0167] The synthesis of the comparative compound, FIMA1, is disclosed in WO2014/015935 A2 (compound 2-8 in example 2).

    B) Device Examples

    [0168] Examples E1 to E5 which follow (see table 1) present the use of the materials of the invention in OLEDs.

    [0169] Pretreatment for Examples E1-E5 Glass plates coated with structured ITO (indium tin oxide) of thickness 50 nm are treated prior to coating with an oxygen plasma, followed by an argon plasma. These plasma-treated glass plates form the substrates to which the OLEDs are applied.

    [0170] 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 aluminium layer of thickness 100 nm. 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. The data of the OLEDs are listed in table 3.

    [0171] All materials are applied by thermal vapour 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:IC2:TEG1 (59%:29%:12%) mean here that the material IC1 is present in the layer in a proportion by volume of 49%, IC2 in a proportion of 44% and TEG1 in a proportion of 7%.

    [0172] Analogously, the electron transport layer may also consist of a mixture of two materials.

    [0173] The OLEDs are characterized in a standard manner. For this purpose, the electroluminescence spectra, the current efficiency (CE, measured in cd/A) and the external quantum efficiency (EQE, measured in %) are determined as a function of luminance, calculated from current-voltage-luminance characteristics assuming Lambertian emission characteristics, as is the lifetime. The electroluminescence spectra are determined at a luminance of 1000 cd/m.sup.2, and the CIE 1931 x and y colour coordinates are calculated therefrom. The parameter U1000 in table 3 refers to the voltage which is required for a luminance of 1000 cd/m. CE1000 and EQE1000 respectively denote the current efficiency and external quantum efficiency that are attained at 1000 cd/m.sup.2.

    [0174] The lifetime LT is defined as the time after which the luminance drops from the starting luminance to a certain proportion L1 in the course of operation with constant current density j0. A figure of L1=80% in table 3 means that the lifetime reported in the LT column corresponds to the time after which the luminance falls to 80% of its starting value.

    [0175] The inventive compounds EG1, EG2, EG3, EG4 are used in examples E2, E3, E4 and E5 as electron blocker material in phosphorescent green OLEDs. The results are compared with the comparative example E1. Table 3 summarizes the performance data of the OLEDs.

    TABLE-US-00008 TABLE 1 Structure of the OLEDs HIL HTL EBL EML HBL ETL EIL Ex. thickness thickness thickness thickness thickness thickness thickness E1 HATCN SpMA1 FIMA1 IC1:IC2:TEG1 ST2 ST2:LiQ (50%:50%) LIQ 5 nm 230 nm 10 nm (59%:29%:12%) 30 nm 10 nm 30 nm 1 nm E2 HATCN SpMA1 EG1 IC1:IC2:TEG1 ST2 ST2:LiQ (50%:50%) LIQ 5 nm 230 nm 10 nm (59%:29%:12%) 30 nm 10 nm 30 nm 1 nm E3 HATCN SpMA1 EG2 IC1:IC2:TEG1 ST2 ST2:LiQ (50%:50%) LIQ 5 nm 230 nm 10 nm (59%:29%:12%) 30 nm 10 nm 30 nm 1 nm E4 HATCN SpMA1 EG3 IC1:IC2:TEG1 ST2 ST2:LiQ (50%:50%) LIQ 5 nm 230 nm 10 nm (59%:29%:12%) 30 nm 10 nm 30 nm 1 nm E5 HATCN SpMA1 EG4 IC1:IC2:TEG1 ST2 ST2:LiQ (50%:50%) LIQ 5 nm 230 nm 10 nm (59%:29%:12%) 30 nm 10 nm 30 nm 1 nm

    TABLE-US-00009 TABLE 2 Structural formulae of the materials for the OLEDs [00765]embedded image [00766]embedded image HATCN SpMA1 [00767]embedded image [00768]embedded image FIMA1 ST2 [00769]embedded image [00770]embedded image LiQ EG1 [00771]embedded image [00772]embedded image EG2 EG3 [00773]embedded image [00774]embedded image EG4 TEG1 [00775]embedded image [00776]embedded image IC1 IC2

    TABLE-US-00010 TABLE 3 Data of the OLEDs U1000 SE1000 EQE 1000 CIE x/y at j.sub.0 L1 LT Ex. (V) (cd/A) (%) 1000 cd/m.sup.2 (mA/cm.sup.2) (%) (h) E1 3.3 69 19.8 0.36/0.61 20 80 310 E2 3.3 71 20.8 0.36/0.62 20 80 328 E3 3.3 77 21.0 0.36/0.62 20 80 316 E4 3.3 80 21.5 0.36/0.62 20 80 298 E5 3.3 81 21.5 0.36/0.62 20 80 305

    [0176] It is found that OLEDs containing the compounds of the invention have very good performance data; in particular, they show distinctly improved efficiencies over the prior art. Moreover, the voltages and lifetimes are at a very high level.