METHOD FOR THE PRODUCE OF GRANULES

Description

[0001] The present invention describes a method for producing granules containing at least one functional material (FM) that can be used to produce functional layers of electronic devices. The invention further relates to granules obtainable according to the present method and their use for the production of an electronic device.

[0002] Electronic devices containing organic, organometallic, and / or polymer semiconductors are gaining increasing importance, being used in many commercial products due to their cost and performance. Examples include organic-based charge transport materials (e.g., triarylamine-based hole transporters) in copiers, organic or polymeric light-emitting diodes (OLEDs or PLEDs) and in display devices, and organic photoreceptors in copiers. Organic solar cells (O-SC), organic field-effect transistors (O-FETs), organic thin-film transistors (O-TFTs), organic integrated circuits (O-ICs), organic optical amplifiers, and organic laser diodes (O-Lasers) are at an advanced stage of development and could become very important in the future.

[0003] Sublimable organic functional materials are frequently used to manufacture these devices. However, the powders and pellets used so far have many disadvantages. Powders generate dust during grinding and transfer, become electrostatically charged, and consequently, an undesirable residue always remains in the container. Furthermore, powders have a low bulk density. Pellets are very complex to produce, making them expensive. Typically, pellets are made from ground powder, so the aforementioned disadvantages are also present, and several process steps are required. Additionally, the pellets are transferred individually and can be fragile. Moreover, the dust problem is not completely resolved. Due to the dust content, increased occupational safety measures are necessary.

[0004] Even in evaporation systems, where vaporization occurs from a melt, problems arise regarding dosing, as the melt must first be maintained. Depending on the system, powders or pellets are used, so the previously described problem also exists.

[0005] Known powders and pellets used in the manufacture of electronic devices exhibit a usable property profile. However, there is a continuing need to improve the properties of these materials and devices. Methods for producing granules are already disclosed in documents US 4,400,191 A, DE 17 67 615 A1, EP 2 014 355 A1, DE 236 477 C and US 2008 / 268245 A1.

[0006] These properties include, in particular, the processability, transportability, and storability of materials used in the manufacture of electronic devices. Specifically, the materials should have a very low dust content and be cost-effective to produce. Furthermore, the processing of these materials should not require particularly stringent occupational safety measures.

[0007] Furthermore, the lifespan of the electronic devices and other properties thereof should not be adversely affected by the aforementioned improvements to the materials. This includes, among other things, the energy efficiency with which an electronic device performs its given task. For organic light-emitting diodes (OLEDs), in particular, the luminous efficacy should be high, so that as little electrical power as possible is required to achieve a specific luminous flux. Additionally, the lowest possible voltage should be necessary to achieve a given luminance.

[0008] Another task can be seen as providing electronic devices with excellent performance as cost-effectively as possible and in consistent quality.

[0009] Furthermore, the electronic devices should be usable or adaptable for many purposes. In particular, the performance of the electronic devices should be maintained over a wide temperature range.

[0010] The object of the present invention is further to provide materials which are suitable for use in an organic electronic device, in particular in an organic electroluminescence device, and which lead to good device properties when used in this device, as well as to provide the corresponding electronic device.

[0011] Surprisingly, it was found that certain methods, described in more detail below, solve these problems and eliminate the disadvantage of the prior art. The formation of fines can be avoided if the material is brought from the melt into a dosable form. This allows for improvements, in particular, with regard to the processability, transportability, and storability of materials for the manufacture of electronic devices. The use of granules leads to very good properties of organic electronic devices, especially organic electroluminescent devices, particularly with regard to lifetime, efficiency, and operating voltage. Electronic devices, especially organic electroluminescent devices, obtained from such granules, as well as the corresponding preferred embodiments, are therefore the subject of the present invention.

[0012] The present invention therefore relates to a method for producing granules containing at least one functional material (FM) which can be used for producing functional layers of electronic devices, comprising the steps: A) Preparation of a melt of a functional material that can be used to produce functional layers of electronic devices; B) Transferring the melt obtained in step A) into a culvert; C) Cooling the melt transferred to the culvert according to step B). obtaining granules, wherein the pressure at which the melt is transferred into a drop tube according to step B) is higher than the pressure in the drop tube, wherein the pressure in the feed vessel is in the range of 400 to 700 mbar and the absolute pressure in the drop tube is in the range of 250 to 500 mbar, wherein the melt transferred into the drop tube according to step B) is cooled with an inert gas in step C), and wherein the granules obtained according to step C) have a fine fraction formed by particles with a diameter of less than 0.1 mm of less than 0.1 wt.%.

[0013] The functional material (FM) used to produce the granules, which can be used to produce functional layers of electronic devices, may preferably be selected from the group consisting of fluorescent emitters, phosphorescent emitters, thermally activated delayed fluorescence (TADF) emitters, host materials, TADF host materials, electron transport materials, exciton blocking materials, electron injection materials, hole guide materials, hole injection materials, n-doped particles, p-doped particles, wide-band gap materials (i.e., materials with a large gap between the HOMO and LUMO energy levels, wherein the gap is preferably greater than or equal to 2.8 eV, very preferably greater than or equal to 3.0 eV, particularly preferably greater than or equal to 3.3 eV, and most preferably greater than or equal to 3.0 eV).5 eV), electron-blocking materials, hole-blocking materials, and / or materials possessing liquid-crystalline properties. These functional materials (FM) can be used individually or as a mixture, or be contained within the granules. The functional material (FM) suitable for fabricating functional layers of electronic devices is preferably an organic material or comprises an organic compound. Organic compounds contain carbon atoms and preferably hydrogen atoms.

[0014] TADF emitters and TADF hosts are well known in the prior art and are disclosed, for example, in Ye Tao et al., Adv. Mater. 2014, 26, 7931-7958, MY Wong et al., Adv. Mater. 2017, 29, 1605444, WO 2011 / 070963, WO 2012 / 133188, WO 2015 / 022974 and WO 2015 / 098975. Typically, TADF emitters and hosts exhibit a very small difference between the S1 singlet and T1 triplet energy states. Preferably, ΔE ST is less than or equal to 0.5 eV for these materials, more preferably less than or equal to 0.3 eV and particularly preferably less than or equal to 0.2 eV, where ΔE ST is the distance between the S 1 energy level and the T 1 energy level.

[0015] The functional material (FM) can, for example, be provided as a powder. Preferably, unmilled sublimate or solidified melt is used. However, the process according to the invention can particularly preferably be carried out as a step in the production of these functional materials. Preferably, therefore, the melt is provided by a production process of the functional material (FM).

[0016] Preferably, the functional material (FM) that can be used to produce functional layers of electronic devices can be melted without decomposition above a temperature of 50°C.

[0017] Furthermore, it can be provided that the functional material (FM), which can be used to produce functional layers of electronic devices, exhibits a degradation of at most 0.1 wt.% in the molten state at processing temperature over a storage period of 10 hours. The processing temperature can be in the range of 50°C to 500°C. Preferably, the functional material (FM), which can be used to produce functional layers of electronic devices, exhibits a degradation of at most 0.1 wt.% in the molten state at a temperature below 50°C above the melting point over a storage period of 10 hours.

[0018] The functional material (FM) provided in step A) is transferred under overpressure into a downpipe. Overpressure means that the pressure in the downpipe is lower than in the feed vessel used to supply the melt. Preferably, the pressure in the feed vessel is at least 10 mbar, more preferably at least 20 mbar, and particularly preferably at least 50 mbar higher than in the downpipe. In a particular embodiment, the pressure in the feed vessel is at most 300 mbar higher than in the downpipe.

[0019] Preferably, the melt transferred to the downpipe according to step B) is cooled with an inert gas in step C). The inert gas preferably has a temperature of no more than 0°C and is preferably in the range of -250 to -20°C, and particularly preferably in the range of -200 to -70°C.

[0020] Inert gases are gases that do not react with the functional materials (FM) under the process conditions. Preferably, the inert gas is nitrogen or a noble gas, in particular helium, argon, neon, xenon, krypton, or a mixture, especially preferably consisting of these gases.

[0021] Furthermore, it can be provided that the melt transferred to the downpipe according to step B) is cooled in step C) over a drop height of at least 50 cm, preferably at least 80 cm. Cooling over a drop height in the range of 80 to 1500 cm is particularly preferred, and especially 100 to 800 cm.

[0022] Preferably, the melt in step B) is transferred through a nozzle into the downpipe. The melt can be introduced into the downpipe via one or more nozzles, the spacing of which is preferably selected such that the melt introduced into the downpipe via different nozzles cannot merge. The nozzle preferably has a diameter of at most 0.9 mm, more preferably at most 0.7 mm, and most preferably at most 0.6 mm. Preferably, the diameter of the nozzle is in the range of 0.1 to 0.5 mm, and more preferably in the range of 0.2 to 0.3 mm.

[0023] In a particular embodiment, the melt is preferably transferred into the downpipe in step B) with a volume flow rate in the range of 0.1 mL per minute to 250 mL per minute, particularly preferably in the range of 1 mL per minute to 150 mL per minute.

[0024] Furthermore, the granules obtained according to step C) may preferably have a diameter in the range of 0.1 to 5 mm, measured by optical methods as a numerical mean. In a further embodiment, the granules obtained according to step C) preferably have a diameter in the range of 0.1 to 5 mm, measured by the sieving method, wherein at least 90%, and particularly preferably at least 99%, of the granule particles have a diameter in the range of 0.1 to 5 mm, the percentage referring to the number of particles.

[0025] Preferably, the granules may be spherical. Within the scope of the present invention, the term "spherical" means that the particles preferably have a spherical shape, whereby it is obvious to those skilled in the art that, due to the process parameters, particles with other shapes may also be present, or that the shape of the particles may deviate from the ideal spherical shape.

[0026] Accordingly, the term spherical means that the ratio of the largest to the smallest particle dimensions is at most 4, preferably at most 2, with these dimensions being measured through the center of mass of the particles. Preferably, at least 70%, and particularly preferably at least 90%, of the particles are spherical.

[0027] For non-spherical granules, the aforementioned diameters refer to the smallest dimension of the granule particles.

[0028] Furthermore, it can be provided that the granules obtained according to step C) have a bulk density of at least 0.6 g / cm³. Preferably, the ratio of the bulk density of the granules to the density of the material used to produce the granules is at least 1:2, more preferably at least 2:3, more preferably at least 3:4, and most preferably at least 5:6.

[0029] In a further embodiment, the functional material (FM) which can be used to produce functional layers of electronic devices is preferably selected from the group consisting of phenyls, fluorenes, indenofluorenes, spirobifluorenes, carbazoles, indenocarbazoles, indolocarbazoles, spirocarbazoles, pyrimidines, triazines, lactams, triarylamines, dibenzofurans, dibenzothienes, imidazoles, benzimidazoles, benzoxazoles, benzthiazoles, 5-aryl-phenanthridin-6-ones, 9,10-dehydrophenanthrenes, fluoranthenes, anthracenes, benzanthracenes, and fluoradenes.

[0030] The functional materials (FM) used to manufacture the granules in question are often organic compounds that provide the functions mentioned above and below. Therefore, the terms functional compound and functional material are often used synonymously.

[0031] Organic functional materials (FMs) are often described by the properties of their frontier orbitals, which are explained in more detail below. Molecular orbitals, in particular the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO), their energy levels, and the energy of the lowest triplet state T1 and the lowest excited singlet state S1 of the materials are determined by quantum chemical calculations. For the calculation of organic substances without metals, a geometry optimization is first performed using the method "Ground State / Semi-Empirical / Default Spin / AM1 / Charge 0 / Spin Singlet". Subsequently, an energy calculation is performed based on the optimized geometry. Here, the method "TD-SCF / DFT / Default Spin / B3PW91" with the basis set "6-31 G(d)" (Charge 0, Spin Singlet) is used.For metal-containing compounds, the geometry is optimized using the method "Ground State / Hartree-Fock / Default Spin / LanL2MB / Charge 0 / Spin Singlet". The energy calculation is analogous to the method described above for organic substances, with the difference that the basis set "LanL2DZ" is used for the metal atom and the basis set "6-31G(d)" for the ligands. The energy calculation yields the HOMO energy level HEh and the LUMO energy level LEh in Hartree units. From these, the HOMO and LUMO energy levels, calibrated using cyclic voltammetry measurements, are determined in electron volts as follows: HOMO eV = HEh * 27.212 − 0.9899 / 1.1206 LUMO eV = LEh * 27.212 − 2.0041 / 1.385

[0032] For the purposes of this application, these values ​​are to be regarded as HOMO or LUMO energy levels of the materials.

[0033] The lowest triplet state T 1 is defined as the energy of the triplet state with the lowest energy, which results from the described quantum chemical calculation.

[0034] The lowest excited singlet state S 1 is defined as the energy of the lowest-energy excited singlet state resulting from the quantum chemical calculation described.

[0035] The method described herein is independent of the software package used and always yields the same results. Examples of commonly used programs for this purpose are "Gaussian09W" (Gaussian Inc.) and Q-Chem 4.1 (Q-Chem, Inc.).

[0036] Compounds with hole injection properties, hereafter also called hole injection materials, facilitate or enable the transfer of holes, i.e., positive charges, from the anode into an organic layer. Generally, a hole injection material has a HOMO level that is at or above the level of the anode, i.e., generally at least -5.3 eV.

[0037] Compounds with hole transport properties, also referred to herein as hole transport materials, are capable of transporting holes, i.e., positive charges, which are generally injected from the anode or an adjacent layer, for example, a hole injection layer. A hole transport material generally exhibits a high HOMO level, preferably at least -5.4 eV. Depending on the design of an electronic device, a hole transport material can also be used as a hole injection material.

[0038] Preferred compounds exhibiting hole injection and / or hole transport properties include, for example, triarylamine, benzidine, tetraaryl-para-phenylenediamine, triarylphosphine, phenothiazine, phenoxazine, dihydrophenazine, thianthrene, dibenzo-pararadioxine, phenoxathiine, carbazole, azulene, thiophene, pyrrole and furan derivatives and other O-, S- or N-containing heterocycles with a high-lying HOMO (HOMO = highest occupied molecular orbital).

[0039] Particularly noteworthy as compounds exhibiting hole injection and / or hole transport properties are phenylenediamine derivatives (US 3615404), arylamine derivatives (US 3567450), amino-substituted chalcone derivatives (US 3526501), styrylanthracene derivatives (JP-A-56-46234), polycyclic aromatic compounds (EP 1009041), polyarylalkane derivatives (US 3615402), fluorenone derivatives (JP-A-54-110837), hydrazone derivatives (US 3717462), acylhydrazones, stilbene derivatives (JP-A-61-210363), silazane derivatives (US 4950950), and polysilanes (JP-A-2-204996). Aniline copolymers (JP-A-2-282263), thiophene oligomers (JP Heisei 1 (1989) 211399), polythiophenes, poly(N-vinylcarbazole) (PVK), polypyrroles, polyanilines and other electrically conductive macromolecules, porphyrin compounds (JP-A-63-2956965, US 4720432), aromatic dimethylidene-type compounds, carbazole compounds such as CDBP, CBP, mCP, aromatic tertiary amine and styrylamine compounds (US 4127412) such asBenzidine-type triphenylamines, styrylamine-type triphenylamines, and diamine-type triphenylamines are suitable. Arylamine dendrimers can also be used (JP Heisei 8 (1996) 193191), as can monomeric triarylamines (US 3180730), triarylamines with one or more vinyl radicals and / or at least one functional group with an active hydrogen (US 3567450 and US 3658520), or tetraaryldiamines (the two tertiaryamine units are linked via an aryl group). Even more triarylamino groups may be present in the molecule. Phthalocyanine derivatives, naphthalocyanine derivatives, butadiene derivatives, and quinoline derivatives such as dipyrazino[2,3-f:2',3'-h]quinoxalinehexacarbonitrile are also suitable.

[0040] Preferred are aromatic tertiary amines with at least two tertiary amine units (US 2008 / 0102311 A1, US 4720432 and US 5061569), such as NPD (α-NPD = 4,4'-bis[N-(1-naphthyl)-N-phenyl-amino]biphenyl) (US 5061569), TPD 232 (= N,N'-Bis-(N,N'-diphenyl-4-aminophenyl)-N,N-diphenyl-4,4'-diamino-1,1'-biphenyl) or MTDATA (MTDATA or m-MTDATA = 4,4',4"-Tris[3-methylphenyl)phenyl-amino]triphenylamine) (JP-A-4-308688), TBDB (= N,N,N',N'-Tetra(4-biphenyl)diaminobiphenylene), TAPC (= 1,1-bis(4-di-p-tolylaminophenyl)-cyclohexane), TAPPP (= 1,1-bis(4-di-p-tolylaminophenyl)-3-phenylpropane), BDTAPVB (= 1,4-Bis[2-[4-[N,N-di(p-tolyl)amino]phenyl]vinyl]benzene), TTB (= N,N,N',N'-tetra- p-tolyl-4,4'-diaminobiphenyl), TPD (= 4,4'-Bis[N-3-methylphenyl]-N-phenylamino)biphenyl), N,N,N',N'-Tetraphenyl-4,4"'-diamino-1,1',4',1",4",1"'-quaterphenyl, as well as tertiary amines with carbazole units such as TCTA (= 4-(9H-carbazol-9-yl)-N,N-bis[4-(9H-carbazol-9-yl)phenyl]benzenamine). Also preferred are hexaaza-triphenylene compounds according to US 2007 / 0092755 A1 and phthalocyanine derivatives (e.g. H 2 Pc, CuPc (= copper phthalocyanine), CoPc, NiPc, ZnPc, PdPc, FePc, MnPc, ClAlPc, ClGaPc, ClInPc, ClSnPc, Cl 2 SiPc, (HO)AlPc, (HO)GaPc, VOPc, TiOPc, MoOPc, GaPc-O-GaPc).

[0041] Particularly preferred are the following triarylamine compounds according to formulas (TA-1) to (TA-6), which are described in documents EP 1162193 B1, EP 650 955 B1, Synth.Metals 1997, 91(1-3), 209, DE 19646119 A1, WO 2006 / 122630 A1, EP 1 860 097 A1, EP 1834945 A1, JP 08053397 A, US 6251531 B1, US 2005 / 0221124, JP 08292586 A, US 7399537 B2, US 2006 / 0061265 A1, EP 1 661 888 and WO 2009 / 041635. The compounds mentioned according to formulas (TA-1) to (TA-6) can also be substituted:

[0042] Other compounds that can be used as hole injection materials are described in EP 0891121 A1 and EP 1029909 A1, injection layers in general in US 2004 / 0174116 A1.

[0043] Preferably, these arylamines and heterocycles, which are generally used as hole injection and / or hole transport materials, lead to a HOMO of more than -5.8 eV (vs. vacuum level), particularly preferably of more than -5.5 eV.

[0044] Compounds exhibiting electron injection and / or electron transport properties include, for example, pyridine, pyrimidine, pyridazine, pyrazine, oxadiazole, quinoline, quinoxaline, anthracene, benzanthracene, pyrene, perylene, benzimidazole, triazine, ketone, phosphine oxide and phenazine derivatives, but also triarylboranes and other O-, S- or N-containing heterocycles with a low LUMO (LUMO = lowest unoccupied molecular orbital).

[0045] Particularly suitable compounds for electron-transporting and electron-injecting layers are metal chelates of 8-hydroxyquinoline (e.g., LiQ, AlQ 3, GaQ 3, MgQ 2, ZnQ 2, InQ 3, ZrQ 4), BAlQ, Ga-oxinoid complexes, 4-azaphenanthrene-5-ol-Be complexes (US 5529853 A, see formula ET-1), butadiene derivatives (US 4356429), heterocyclic optical brighteners (US 4539507), benzimidazole derivatives (US 2007 / 0273272 A1), such as TPBI (US 5766779, see formula ET-2), 1,3,5-triazines, e.g., spirobifluorene-triazine derivatives (e.g., according to the DE). 102008064200), pyrenes, anthracenes, tetracenes, fluorenes, spirofluorenes, dendrimers, tetracenes (e.g. rubrene derivatives), 1,10-phenanthroline derivatives (JP 2003-115387, JP 2004-311184, JP-2001-267080, WO 2002 / 043449), silacyclopentadiene derivatives (EP 1480280, EP 1478032, EP 1469533), borane derivatives such as triarylborane derivatives with Si (US 2007 / 0087219 A1, cf.Formula ET-3), pyridine derivatives (JP 2004-200162), phenanthrolines, especially 1,10-phenanthroline derivatives, such as BCP and Bphen, also several phenanthrolines linked via biphenyl or other aromatic groups (US-2007-0252517 A1) or anthracene-linked phenanthrolines (US 2007-0122656 A1, see formulas ET-4 and ET-5). Heterocyclic organic compounds such as thiopyran dioxides, oxazoles, triazoles, imidazoles, or oxadiazoles are also suitable. Examples of the use of five-membered rings with N such as oxazoles, preferably 1,3,4-oxadiazoles, for example compounds according to formulas ET-6, ET-7, ET-8, and ET-9, which are set out, inter alia, in US 2007 / 0273272 A1; thiazoles, oxadiazoles, thiadiazoles, triazoles, etc., see US 2008 / 0102311 A1 and YA Levin, MS Skorobogatova, Khimiya Geterotsiklicheskikh Soedinenii 1967 (2), 339-341, preferably compounds according to formula ET-10, silacyclopentadiene derivatives. Preferred compounds are the following according to formulas (ET-6) to (ET-10):

[0046] Organic compounds such as derivatives of fluorenone, fluorenylidenemethane, perylenetetracarbonic acid, anthraquinone dimethane, diphenoquinone, anthrone and anthraquinone diethylenediamine can also be used.

[0047] Preferred are 2,9,10-substituted anthracenes (with 1- or 2-naphthyl and 4- or 3-biphenyl) or molecules containing two anthracene units (US 2008 / 0193796 A1, see formula ET-11). The combination of 9,10-substituted anthracene units with benzimidazole derivatives is also very advantageous (US 2006 147747 A and EP 1551206 A1, see formulas ET-12 and ET-13).

[0048] Preferably, the compounds that can generate the electron injection and / or electron transport properties lead to a LUMO of less than -2.5 eV (vs. vacuum level), particularly preferably of less than -2.7 eV.

[0049] The functional materials used to produce the granules in question can include emitters, and the compounds that can be used according to the invention can be configured as emitters. The term emitter refers to a material which, after excitation (which can be effected by the transfer of any type of energy), allows a radiative transition to a ground state with the emission of light. Generally, two classes of emitters are known: fluorescent (including time-delayed fluorescence) and phosphorescent emitters. The term fluorescent emitter refers to materials or compounds in which a radiative transition from an excited singlet state to the ground state occurs. The term phosphorescent emitter preferably refers to luminescent materials or compounds comprising transition metals.

[0050] Emitters are often also referred to as dopants if the dopants cause the previously described properties in a system. In a system containing a matrix material and a dopant, a dopant is understood to be the component whose proportion in the mixture is smaller. Similarly, in a system containing a matrix material and a dopant, a matrix material is understood to be the component whose proportion in the mixture is larger. Therefore, the term phosphorescent emitters can also refer to phosphorescent dopants.

[0051] Compounds capable of emitting light include, among others, fluorescent and phosphorescent emitters. These include compounds with stilbene, stilbenamine, styrylamine, coumarin, rubrene, rhodamine, thiazole, thiadiazole, cyanine, thiophene, paraphenylene, perylene, phthalocyanine, porphyrin, ketone, quinoline, imine, anthracene, and / or pyrene structures. Compounds that can emit light from the triplet state with high efficiency even at room temperature, i.e., exhibit electrophosphorescence instead of electrofluorescence, are particularly preferred, as this often results in increased energy efficiency. Compounds containing heavy atoms with an atomic number greater than 36 are initially suitable for this purpose. Compounds containing d- or f-transition metals that meet the aforementioned condition are preferred. Compounds containing elements from group 8 to 10 (Ru, Os, Rh, Ir, Pd, Pt) are particularly preferred.For example, various complexes are suitable as functional compounds, such as those described in WO 02 / 068435 A1, WO 02 / 081488 A1, EP 1239526 A2 and WO 04 / 026886 A2.

[0052] The following are examples of preferred compounds that can serve as fluorescent emitters. Preferred fluorescent emitters are selected from the classes of monostyrylamines, distyrylamines, tristyrylamines, tetrastyrylamines, styrylphosphines, styryl ethers, and arylamines.

[0053] A monostyrylamine is understood to be a compound containing one substituted or unsubstituted styryl group and at least one, preferably aromatic, amine. A distyrylamine is understood to be a compound containing two substituted or unsubstituted styryl groups and at least one, preferably aromatic, amine. A tristyrylamine is understood to be a compound containing three substituted or unsubstituted styryl groups and at least one, preferably aromatic, amine. A tetrastyrylamine is understood to be a compound containing four substituted or unsubstituted styryl groups and at least one, preferably aromatic, amine. The styryl groups are particularly preferably stilbenes, which may also be further substituted. Corresponding phosphines and ethers are defined analogously to the amines. An arylamine, or...An aromatic amine within the meaning of the present invention is understood to be a compound containing three substituted or unsubstituted aromatic or heteroaromatic ring systems directly bonded to the nitrogen atom. Preferably, at least one of these aromatic or heteroaromatic ring systems is a condensed ring system, preferably with at least 14 aromatic ring atoms. Preferred examples are aromatic anthracene amines, aromatic anthracene diamines, aromatic pyrene amines, aromatic pyrenediamines, aromatic chrysene amines, or aromatic chrysenediamines. An aromatic anthracene amine is understood to be a compound in which a diarylamine group is directly bonded to an anthracene group, preferably at the 9-position. An aromatic anthracene diamine is understood to be a compound in which two diarylamine groups are directly bonded to an anthracene group, preferably at the 2,6- or 9,10-position.Aromatic pyrenamines, pyrendiamines, chrysenamines and chrysendiamines are defined analogously, wherein the diarylamine groups on the pyrene are preferably bonded in the 1-position or in the 1,6-position.

[0054] Other preferred fluorescent emitters are selected from indenofluorenamines or diamines, which are set out, inter alia, in document WO 06 / 122630; benzoindenofluorenamines or diamines, which are set out, inter alia, in document WO 2008 / 006449; and dibenzoindenofluorenamines or diamines, which are set out, inter alia, in document WO 2007 / 140847.

[0055] Examples of compounds from the styrylamine class that can be used as fluorescent emitters include substituted or unsubstituted tristilbenamines or the dopants described in WO 06 / 000388, WO 06 / 058737, WO 06 / 000389, WO 07 / 065549, and WO 07 / 115610. Distyrylbenzene and distyrylbiphenyl derivatives are described in US 5121029. Further styrylamines can be found in US 2007 / 0122656 A1.

[0056] Particularly preferred styrylamine compounds are the compounds of formula EM-1 described in US 7250532 B2 and the compounds of formula EM-2 presented in DE 10 2005 058557 A1:

[0057] Particularly preferred triarylamine compounds, groups or structural elements are the compounds of formulas EM-3 to EM-15 and their derivatives set out in documents CN 1583691 A, JP 08 / 053397 A and US 6251531 B1, EP 1957606 A1, US 2008 / 0113101 A1, US 2006 / 210830 A , WO 08 / 006449 and DE 102008035413:

[0058] Other preferred compounds that can be used as fluorescent emitters are selected from derivatives of naphthalene, anthracene, tetracene, benzanthracene, benzphenanthrene (DE 10 2009 005746), fluorene, fluoranthene, periflanthene, indenoperylene, phenanthrene, perylene (US 2007 / 0252517 A1), pyrene, chrysene, decacyclene, coronene, tetraphenylcyclopentadiene, pentaphenylcyclopentadiene, fluorene, spirofluorene, rubrene, coumarin (US 4769292, US 6020078, US 2007 / 0252517 A1), pyran, oxazole, benzoxazole, benzothiazole, benzimidazole, pyrazine, cinnamic acid esters, diketopyrrolopyrrole, acridone, and quinacridone (US 2007 / 0252517 A1).

[0059] Of the anthracene compounds, those substituted at the 9,10 position, such as 9,10-diphenylanthracene and 9,10-bis(phenylethynyl)anthracene, are particularly preferred. 1,4-Bis(9'-ethynylanthraceneyl)benzene is also a preferred dopant.

[0060] Also preferred are derivatives of rubrene, coumarin, rhodamine, quinacridone such as DMQA (= N,N'-dimethylquinacridone), dicyanomethylenepyran such as DCM (= 4-(dicyanoethylene)-6-(4-dimethylamino-styryl-2-methyl)-4H-pyran), thiopyran, polymethine, pyrylium and thiapyrylium salts, periflanthen and indenoperylene.

[0061] Blue fluorescent emitters are preferably polyaromatics such as 9,10-di(2-naphthylanthracene) and other anthracene derivatives, derivatives of tetracene, xanthene, perylene such as 2,5,8,11-tetra- t -butyl-ρerylene, phenylene, e.g. 4,4'-(Bis(9-ethyl-3-carbazovinylene)-1,1'-biphenyl, fluorene, fluoranthene, arylpyrene (US 2006 / 0222886 A1), arylenevinylene (US 5121029, US 5130603), bis(azinyl)imine boron compounds (US 2007 / 0092753 A1), bis(azinyl)methene compounds and carbostyryl compounds.

[0062] Other preferred blue fluorescent emitters are described in CHChen et al.: "Recent developments in organic electroluminescent materials" Macromol. Symp. 125, (1997) 1-48 and "Recent progress of molecular organic electroluminescent materials and devices" Mat. Sci. and Eng. R, 39 (2002), 143-222.

[0063] Other preferred blue fluorescent emitters are the hydrocarbons disclosed in DE 102008035413. Particularly preferred are also the compounds described in WO 2014 / 111269, especially compounds with a bis-indienofluorene backbone.

[0064] The following are examples of preferred compounds that can serve as phosphorescent emitters.

[0065] Examples of phosphorescent emitters can be found in WO 00 / 70655, WO 01 / 41512, WO 02 / 02714, WO 02 / 15645, EP 1191613, EP 1191612, EP 1191614, and WO 05 / 033244. In general, all phosphorescent complexes used in phosphorescent OLEDs according to the prior art and known to those skilled in the art in the field of organic electroluminescence are suitable, and those skilled in the art can use other phosphorescent complexes without inventive effort. Phosphorescent metal complexes preferably contain Ir, Ru, Pd, Pt, Os, or Re.

[0066] Preferred ligands are 2-phenylpyridine derivatives, 7,8-benzoquinoline derivatives, 2-(2-thienyl)pyridine derivatives, 2-(1-naphthyl)pyridine derivatives, 1-phenylisoquinoline derivatives, 3-phenylisoquinoline derivatives, or 2-phenylquinoline derivatives. All of these compounds can be substituted, e.g., for blue, with fluorine, cyano, and / or trifluoromethyl substituents. Auxiliary ligands are preferably acetylacetonate or picolinic acid.

[0067] In particular, complexes of Pt or Pd with tetradentate ligands according to formula EM-16 are suitable as emitters.

[0068] The compounds according to formula EM-16 are described in more detail in US 2007 / 0087219 A1, and reference is made to this publication for disclosure purposes to explain the substituents and indices in the above formula. Furthermore, Pt-porphyrin complexes with an enlarged ring system (US 2009 / 0061681 A1) and Ir complexes are suitable, e.g., 2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphyrin-Pt(II), tetraphenyl-Pt(II)-tetrabenzoporphyrin (US 2009 / 0061681 A1), cis-bis(2-phenylpyridinato-N,C2<')Pt(II). cis -Bis(2-(2'-thienyl)pyridinato-N,C 3< ')Pt(II), cis-Bis-(2-(2'-thienyl)chinolinato-N,C 5< ')Pt(II), (2-(4,6-Difluoro-phenyl)pyridinato-N,C 2< ')Pt(II)(acetylacetonat), oder Tris(2-phenylpyridinato-N,C 2< ')Ir(III) (= Ir(ppy) 3 , grün), Bis(2-phenyl-pyridinato-N,C 2< )Ir(III)(acetylacetonat) (= Ir(p P y) 2 acetylacetonat, grün, US 2001 / 0053462 A1, Baldo, Thompson et al. Nature 403, (2000), 750-753), Bis(1-phenylisochinolinato-N,C 2< ')(2-phenylpyridinato-N,C 2< ')Iridium(III), Bis(2-phenylpyridinato-N,C 2< ')(1-phenylisochinolinato-N,C 2< ')Iridium(III), Bis(2-(2'-benzothienyl)pyridinato-N,C 3< ')Iridium(III)(acetylacetonat), Bis(2-(4',6'-difluorophenyl)pyridinato-N,C 2< ')Iridium(III)(piccolinat) (FIrpic, blau), Bis(2-(4',6'-difluorophenyl)-pyridinato-N,C 2< ')Ir(III)(tetrakis(1-pyrazolyl)borat), Tris(2-(biphenyl-3-yl)-4-tertbutylpyridin)iridium(III), (ppz) 2 Ir(5ρhdpym) (US 2009 / 0061681 A1), (45ooppz) 2 Ir(5ρhdpym) (US 2009 / 0061681 A1), Derivate von 2-Phenylpyridin-Ir-Komplexen, wie z.B.PQIr (= Iridium(III)-bis(2-phenyl-quinolyl-N,C 2< ')acetylacetonate), Tris(2-phenylisoquinolinato-N,C)Ir(III) (red), Bis(2-(2'-benzo[4,5-a]thienyl)pyridinato-N C 3< ) Ir(acetyl-acetonate) ( [Btp 2 Ir(acac)], red, Adachi et al. Appl. Phys. Lett. 78 (2001), 1622-1624). The complexes described in WO 2016 / 124304 are also particularly suitable.

[0069] Also suitable are complexes of trivalent lanthanides such as Tb 3+< and Eu 3+< (J. Kido et al. Appl. Phys. Lett. 65 (1994), 2124, Kido et al. Chem. Lett. 657, 1990, US 2007 / 0252517 A1) or phosphorescent complexes of Pt(II), Ir(I), Rh(I) with maleonitrile dithiolate (Johnson et al., JACS 105, 1983, 1795), Re(I)-tricarbonyl-diimine complexes (Wrighton, JACS 96, 1974, 998 et al.), Os(II) complexes with cyano ligands and bipyridyl or phenanthroline ligands (Ma et al., Synth. Metals 94, 1998, 245).

[0070] Other phosphorescent emitters with tridentate ligands are described in US 6824895 and US 10 / 729238. Red-emitting phosphorescent complexes are found in US 6835469 and US 6830828.

[0071] Particularly preferred compounds used as phosphorescent dopants include those described in US 2001 / 0053462 A1 and Inorg. Chem. 2001, 40(7), 1704-1711, JACS 2001, 123(18), 4304-4312, according to formula EM-17, and derivatives thereof.

[0072] Derivatives are described in US 7378162 B2, US 6835469 B2 and JP 2003 / 253145 A.

[0073] Furthermore, the compounds described in US 7238437 B2, US 2009 / 008607 A1 and EP 1348711 according to formula EM-18 to EM-21 and their derivatives can be used as emitters.

[0074] Quantum dots can also be used as emitters, and these materials are disclosed in detail in WO 2011 / 076314 A1.

[0075] Compounds used as host materials, especially together with emitting compounds, include materials from various classes of substances.

[0076] Host materials generally exhibit larger band gaps between the HOMO and LUMO than the emitter materials used. Additionally, preferred host materials display either hole-transport or electron-transport properties. Furthermore, host materials can exhibit both electron- and hole-transport properties.

[0077] Host materials are sometimes also referred to as matrix materials, especially if the host material is used in combination with a phosphorescent emitter in an OLED.

[0078] Preferred host materials or co-host materials, which are used particularly in conjunction with fluorescent dopants, are selected from the classes of oligoarylenes (e.g., 2,2',7,7'-tetraphenylspirobifluorene according to EP 676461 or dinaphthylanthracene), in particular oligoarylenes containing fused aromatic groups such as anthracene, benzanthracene, benzphenanthrene (DE 10 2009 005746, WO 09 / 069566), phenanthrene, tetracene, coronene, chrysene, fluorene, spirofluorene, perylene, phthaloperylene, naphthaloperylene, decacyclene, rubrene, the oligoarylene vinylenes (e.g., DPVBi = 4,4'-bis(2,2-diphenyl-ethenyl)-1,1'-biphenyl) or Spiro-DPVBi according to EP 676461), the polypodal metal complexes (e.g. according to WO 04 / 081017), in particular metal complexes of 8-hydroxyquinoline, e.g.AlQ 3 (= aluminum(III)tris(8-hydroxyquinoline)) or bis(2-methyl-8-quinolinolato)-4-(phenylphenolinolato)aluminium, also with imidazole chelate (US 2007 / 0092753 A1) as well as the quinoline metal complexes, aminoquinoline metal complexes, benzoquinoline metal complexes, the hole-conducting compounds (e.g. according to WO 2004 / 058911), the electron-conducting compounds, in particular ketones, phosphine oxides, sulfoxides, carbazoles, spirocarbazoles, indenocarbazoles, etc. (e.g. according to WO 2005 / 084081 and WO 2005 / 084082), the atropisomers (e.g. according to WO 06 / 048268), the boronic acid derivatives (e.g. according to WO 2006 / 117052) or the benzanthracene (e.g. according to WO 2008 / 145239).

[0079] Particularly preferred compounds that can serve as host materials or co-host materials are selected from the classes of oligoarylenes containing anthracene, benzanthracene, and / or pyrene, or atropisomers of these compounds. For the purposes of this invention, an oligoarylene is understood to be a compound in which at least three aryl or arylene groups are bonded together. Preferred host materials are particularly selected from compounds of the formula (H-100), Ar5< -(Ar6< ) p -Ar7< (H-100), where Ar5< , Ar6< , Ar7< , in each instance, is the same or different an aryl or heteroaryl group with 5 to 30 aromatic ring atoms, which may optionally be substituted, and p is an integer in the range of 1 to 5. The sum of the π electrons in Ar 5< , Ar 6< and Ar 7< is at least 30 when p = 1, at least 36 when p = 2, and at least 42 when p = 3.

[0080] Particularly preferably, in the compounds of formula (H-100), the group Ar 6< represents anthracene, and the groups Ar 5< and Ar 7< are bonded at the 9- and 10-positions, respectively, and these groups may optionally be substituted. Most preferably, at least one of the groups Ar 5< and / or Ar 7< is a fused aryl group selected from 1- or 2-naphthyl, 2-, 3- or 9-phenanthrenyl, or 2-, 3-, 4-, 5-, 6- or 7-benzanthracenyl. Anthracene-based compounds are described in US 2007 / 0092753 A1 and US 2007 / 0252517 A1, e.g. 2-(4-methylphenyl)-9,10-di-(2-naphthyl)anthracene, 9-(2-naphthyl)-10-(1,1'-biphenyl)anthracene and 9,10-bis[4-(2,2-diphenylethenyl)phenyl]anthracene, 9,10-diphenylanthracene, 9,10-bis(phenylethynyl)anthracene and 1,4-bis(9'-ethynylanthracenyl)benzene. Compounds with two anthracene units are also preferred (US 2008 / 0193796 A1), e.g. 10,10'-Bis[1,1',4', 1"]terphenyl-2-yl-9,9'-bisanthracenyl.

[0081] Other preferred compounds are derivatives of arylamine, styrylamine, fluorescein, diphenylbutadiene, tetraphenylbutadiene, cyclopentadiene, tetraphenylcyclopentadiene, pentaphenylcyclopentadiene, coumarin, oxadiazole, bisbenzoxazoline, oxazole, pyridine, pyrazine, imine, benzothiazole, benzoxazole, benzimidazole (US 2007 / 0092753 A1), e.g., 2,2',2"-(1,3,5-phenylene)tris[1-phenyl-1H-benzimidazole], aldazine, stilbene, styrylarylene derivatives, e.g., 9,10-bis[4-(2,2-diphenylethenyl)phenyl]anthracene and distyrylarylene derivatives (US 5121029), diphenylethylene, vinylanthracene, diaminocarbazole, pyran, thiopyran. Diketopyrrolopyrrole, polymethin, cinnamic acid esters and fluorescent dyes.

[0082] Particularly preferred are derivatives of arylamine and styrylamine, e.g., TNB (= 4,4'-bis[N-(1-naphthyl)-N-(2-naphthyl)amino]biphenyl). Metal-oxinoid complexes such as LiQ or AlQ 3 can be used as co-hosts.

[0083] Preferred compounds with oligoarylenes as a matrix are set out in US 2003 / 0027016 A1, US 7326371 B2, US 2006 / 043858 A, WO 2007 / 114358, WO 08 / 145239, JP 3148176 B2, EP 1009044, US 2004 / 018383, WO 2005 / 061656 A1, EP 0681019B1, WO 2004 / 013073A1, US 5077142, WO 2007 / 065678 and DE 102009005746, with particularly preferred compounds being described by formulas H-102 to H-108.

[0084] Furthermore, compounds that can be used as a host or matrix include materials that are used together with phosphorescent emitters. These compounds, which can also be used as structural elements in polymers, include CBP (N,N-biscarbazolylbiphenyl), carbazole derivatives (e.g., according to WO 05 / 039246, US 2005 / 0069729, JP 2004 / 288381, EP 1205527 or WO 08 / 086851), azacarbazoles (e.g., according to EP 1617710, EP 1617711, EP 1731584, JP 2005 / 347160), ketones (e.g., according to WO 04 / 093207 or according to DE 102008033943), phosphine oxides, sulfoxides and sulfones (e.g., according to WO 05 / 003253), oligophenylenes, and aromatic amines (e.g., according to US 2005 / 0069729), bipolar matrix materials (e.g., according to WO 07 / 137725), silanes (e.g., according to WO 05 / 111172), 9,9-diarylfluorene derivatives (e.g., according to DE 102008017591), azaboroles or boron esters (e.g., according to WO 06 / 117052), triazine derivatives (e.g., according to DE 102008036982), indolocarbazole derivatives (e.g.,according to WO 07 / 063754 or WO 08 / 056746), indenocarbazole derivatives (e.g. according to DE 102009023155 and DE 102009031021), diazaphosphol derivatives (e.g. according to DE 102009022858), triazole derivatives, oxazoles and oxazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazole derivatives, pyrazolone derivatives, distyrylpyrazine derivatives, thiopyran dioxide derivatives, phenylenediamine derivatives, tertiary aromatic amines, styrylamines, amino-substituted chalcone derivatives, indoles, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic dimethylidene compounds, carbodiimide derivatives, metal complexes of 8-Hydroxyquinoline derivatives such as AlQ 3, the 8-hydroxyquinoline complexes may also contain triarylaminophenol ligands (US 2007 / 0134514 A1), metal complex polysilane compounds, as well as thiophene, benzothiophene and dibenzothiophene derivatives.

[0085] Examples of preferred carbazole derivatives are mCP (= 1,3-N,N-dicarbazolebenzene (= 9,9'-(1,3-phenylene)bis-9H-carbazole)) (formula H-9), CDBP (= 9,9'-(2,2'-dimethyl[1,1'-biphenyl]-4,4'-diyl)bis-9H-carbazole), 1,3-bis(N,N'-dicarbazole)benzene (= 1,3-bis(carbazol-9-yl)benzene), PVK (polyvinylcarbazole), 3,5-di(9H-carbazol-9-yl)biphenyl, and CMTTP (formula H10). Particularly preferred compounds are set forth in US 2007 / 0128467 A1 and US 2005 / 0249976 A1 (formulas H-111 to H-113).

[0086] Preferred Si tetraaryls are described, for example, in documents US 2004 / 0209115, US 2004 / 0209116, US 2007 / 0087219 A1 and H. Gilman, EA Zuech, Chemistry & Industry (London, United Kingdom), 1960, 120. Particularly preferred Si tetraaryls are described by formulas H-114 to H-120.

[0087] Particularly preferred compounds for the preparation of the matrix for phosphorescent dopants are set out, among others, in DE 102009022858, DE 102009023155, EP 652273 B1, WO 2007 / 063754 and WO 2008 / 056746, wherein particularly preferred compounds are described by formulas H-121 to H-124.

[0088] With regard to the functional compounds that can be used according to the invention and serve as host materials, substances containing at least one nitrogen atom are particularly preferred. These preferably include aromatic amines, triazine and carbazole derivatives. Carbazole derivatives, in particular, exhibit surprisingly high efficiency. Triazine derivatives unexpectedly lead to long lifetimes of the electronic devices using these compounds.

[0089] It may also be preferred to use several different matrix materials as a mixture, in particular at least one electron-conducting matrix material and at least one hole-conducting matrix material. Equally preferred is the use of a mixture of a charge-transporting matrix material and an electrically inert matrix material, which is not involved, or not to a significant extent, in charge transport, as described, for example, in WO 2010 / 108579.

[0090] Furthermore, compounds can be used that improve the transition from the singlet to the triplet state and, when used in conjunction with functional compounds possessing emitting properties, enhance the phosphorescence properties of these compounds. Carbazole and bridged carbazole dimer units, as described, for example, in WO 04 / 070772 A2 and WO 04 / 113468 A1, are particularly suitable for this purpose. Ketones, phosphine oxides, sulfoxides, sulfones, silane derivatives, and similar compounds, as described, for example, in WO 05 / 040302 A1, are also suitable.

[0091] In this context, n-dotandes are understood to be reducing agents, i.e., electron donors. Preferred examples of n-doped compounds are W(hpp)4 and other electron-rich metal complexes according to WO 2005 / 086251 A2, P=N compounds (e.g., WO 2012 / 175535 A1, WO 2012 / 175219 A1), naphthylene carbodiimides (e.g., WO 2012 / 168358 A1), fluorenes (e.g., WO 2012 / 031735 A1), radicals and diradicals (e.g., EP 1837926 A1, WO 2007 / 107306 A1), pyridines (e.g., EP 2452946 A1, EP 2463927 A1), N-heterocyclic compounds (e.g., WO 2009 / 000237 A1), and acridines as well as phenazines (e.g., US 2007 / 145355 A1).

[0092] Furthermore, the compounds used to produce the granules according to the invention can be designed as wide-band-gap materials. Wide-band-gap materials are understood to be materials as defined in US 7,294,849. These systems exhibit particularly advantageous performance characteristics in electroluminescent devices.

[0093] Preferably, the compound used as a wide-bandgap material can have a band gap of 2.5 eV or more, preferably 3.0 eV or more, and most preferably 3.5 eV or more. The band gap can be calculated, among other methods, from the energy levels of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO).

[0094] Furthermore, the compounds used to produce the granules according to the invention can be configured as hole-blocking material (HBM). A hole-blocking material is a material which, in a multilayer composite, prevents or minimizes the transmission of holes (positive charges), particularly if this material is arranged in the form of a layer adjacent to an emission layer or a hole-conducting layer. In general, a hole-blocking material has a lower HOMO level than the hole-conducting material in the adjacent layer. Hole-blocking layers are frequently arranged between the light-emitting layer and the electron transport layer in OLEDs.

[0095] In principle, any known hole-blocking material can be used. In addition to other hole-blocking materials described elsewhere in this application, suitable hole-blocking materials include metal complexes (US 2003 / 0068528), such as bis(2-methyl-8-quinolinolato)(4-phenylphenolato)-aluminium(III) (BAIQ). Fac-tris(1-phenylpyrazolato-N,C2)iridium(III) (Ir(ppz)3) is also used for this purpose (US 2003 / 0175553 A1). Phenanthroline derivatives, such as BCP, or phthalimides, such as TMPP, can also be used.

[0096] Furthermore, suitable hole-blocking materials are described in WO 00 / 70655 A2, WO 01 / 41512 and WO 01 / 93642 A1.

[0097] Furthermore, the compounds usable according to the invention can be designed as electron blocking materials (EBMs). An electron blocking material is a material which, in a multilayer composite, prevents or minimizes the conduction of electrons, particularly if this material is arranged in the form of a layer adjacent to an emission layer or an electron-conducting layer. In general, an electron blocking material has a higher LUMO level than the electron transport material in the adjacent layer.

[0098] In principle, any known electron-blocking material can be used. In addition to other electron-blocking materials described elsewhere in this application, suitable electron-blocking materials include transition metal complexes such as Ir(ppz)3 (US 2003 / 0175553).

[0099] Preferably, the electron blocking material can be selected from amines, triarylamines and their derivatives.

[0100] Materials possessing liquid-crystalline properties are widely known as such in the scientific community. These materials are used in...

[0101] The application temperature is variable, but the liquid properties vary, while the liquid properties exhibit direction-dependent physical characteristics.

[0102] Furthermore, the functional materials (FM) which can be used to produce functional layers of electronic devices, provided they are low molecular weight compounds, preferably have a molecular weight of ≤ 3000 g / mol, particularly preferably ≤ 2000 g / mol, particularly preferably ≤ 1500 g / mol and most preferably ≤ 1000 g / mol.

[0103] Of particular interest are functional materials (FM) that can be used to produce functional layers of electronic devices and are characterized by a high glass transition temperature. In this context, compounds suitable for producing functional layers of electronic devices are preferred if they have a glass transition temperature of ≥ 70°C, preferably ≥ 100°C, particularly preferably ≥ 125°C, and especially preferably ≥ 150°C, as determined according to DIN 51005:2005-08.

[0104] Provided that the conditions specified in claim 1 are met, the preferred embodiments mentioned above can be combined with one another as desired. In a particularly preferred embodiment of the invention, the preferred embodiments mentioned above apply simultaneously.

[0105] The compounds that can be used according to the invention, which are suitable for producing functional layers of electronic devices, can in principle be produced by various methods, which are described in the aforementioned publications.

[0106] The granules obtainable according to the invention differ from known compositions in that the granules have a fine fraction, formed by particles with a diameter of less than 0.1 mm, of less than 0.1 wt.%.

[0107] Another object of the present invention is therefore a granulate obtainable according to a method of the present invention.

[0108] The granules according to the invention can contain all organically functional materials necessary for the production of the respective functional layer of the electronic device. For example, if a hole transport, hole injection, electron transport, or electron injection layer is composed of precisely one functional compound, then the granule comprises precisely this compound as an organically functional material. If, for example, an emission layer has an emitter in combination with a matrix or host material, then the formulation comprises precisely the mixture of emitter and matrix or host material as an organically functional material, as is explained in more detail elsewhere in the present application. In a preferred embodiment, the granule contains two or more matrix materials (or host materials), most preferably exactly two matrix materials (or host materials).Such mixtures of several matrix or host materials are also known to those skilled in the art as premixed systems.

[0109] Functional materials are generally the organic or inorganic materials that are placed between the anode and the cathode.Preferably, the organically functional material is selected from the group consisting of fluorescent emitters, phosphorescent emitters, emitters exhibiting TADF (thermally activated delayed fluorescence), host materials, electron transport materials, electron injection materials, hole transport materials, hole injection materials, electron blocking materials, hole blocking materials, wide-band-gap materials, p-dotandes, n-dotandes and / or materials possessing liquid-crystalline properties, preferably fluorescent emitters, phosphorescent emitters, emitters exhibiting TADF (thermally activated delayed fluorescence), host materials, electron transport materials, electron injection materials, hole transport materials, hole injection materials, electron blocking materials, hole blocking materials, wide-band-gap materials, p-dotandes and / or n-dotandes.

[0110] Another object of the present invention is the use of granules according to the present invention for the manufacture of an electronic device.

[0111] An electronic device is understood to be a device which contains an anode, a cathode and at least one intermediate functional layer, wherein this functional layer contains at least one organic or organometallic compound.

[0112] The organic electronic device is preferably an organic electroluminescent device (OLED), a polymer electroluminescent device (PLED), an organic integrated circuit (O-IC), an organic field-effect transistor (O-FET), an organic thin-film transistor (O-TFT), an organic light-emitting transistor (O-LET), an organic solar cell (O-SC), an organic optical detector, an organic photoreceptor, an organic field quench device (O-FQD), an organic electrical sensor, a light-emitting electrochemical cell (LEC), an organic laser diode (O-Laser), or a liquid crystal display.

[0113] Active components are generally the organic or inorganic materials inserted between the anode and cathode, whereby these active components determine, maintain, and / or improve the properties of the electronic device, such as its performance and / or its lifetime. Examples include charge injection, charge transport, or charge blocking materials, but especially emission materials and matrix materials. Accordingly, the organically functional material that can be used to produce functional layers of electronic devices preferably comprises an active component of the electronic device.

[0114] A preferred embodiment of the present invention is organic electroluminescent devices. The organic electroluminescent device comprises a cathode, anode, and at least one emitting layer.

[0115] It is also preferred to use a mixture of two or more triplet emitters together with a matrix. The triplet emitter with the shorter-wavelength emission spectrum serves as a co-matrix for the triplet emitter with the longer-wavelength emission spectrum.

[0116] In this case, the proportion of matrix material in the emitting layer is preferably between 50 and 99.9 vol.%, particularly preferably between 80 and 99.5 vol.%, and especially preferably between 92 and 99.5 vol.% for fluorescent emitting layers and between 85 and 97 vol.% for phosphorescent emitting layers.

[0117] Accordingly, the proportion of the dopant is preferably between 0.1 and 50 vol.%, particularly preferably between 0.5 and 20 vol.% and especially preferably between 0.5 and 8 vol.% for fluorescent emitting layers and between 3 and 15 vol.% for phosphorescent emitting layers.

[0118] An emitting layer of an organic electroluminescent device can also comprise systems containing multiple matrix materials (mixed-matrix systems) and / or multiple dopants. In this case, too, the dopants are generally those materials with the smaller proportion in the system, and the matrix materials are those materials with the larger proportion. In some cases, however, the proportion of a single matrix material in the system may be smaller than the proportion of a single dopant.

[0119] The mixed-matrix systems preferably comprise two or three different matrix materials, and more preferably two different matrix materials. Preferably, one of the two materials is a material with hole-transporting properties and the other material is a material with electron-transporting properties. However, the desired electron-transporting and hole-transporting properties of the mixed-matrix components can also be combined mainly or completely in a single mixed-matrix component, with the other mixed-matrix component(s) fulfilling different functions. The two different matrix materials can be present in a ratio of 1:50 to 1:1, preferably 1:20 to 1:1, more preferably 1:10 to 1:1, and more preferably 1:4 to 1:1. Mixed-matrix systems are preferably used in phosphorescent organic electroluminescence devices.More detailed information on mixed matrix systems can be found, for example, in WO 2010 / 108579.

[0120] In addition to these layers, an organic electroluminescent device may contain further layers, for example, one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, exciton blocking layers, electron blocking layers, charge generation layers (IDMC 2003, Taiwan; Session 21 OLED (5), T. Matsumoto, T. Nakada, J. Endo, K. Mori, N. Kawamura, A. Yokoi, J. Kido, Multiphoton Organic EL Device Having Charge Generation Layer) )and / or organic or inorganic p / n junctions. It is possible that one or more hole transport layers are p-doped, for example with metal oxides such as MoO₃ or WO₃, or with (per)fluorinated electron-deficient aromatics, and / or that one or more electron transport layers are n-doped. Likewise, interlayers can be introduced between two emitting layers, which, for example, have an exciton-blocking function and / or control the charge balance in the electroluminescence device. It should be noted, however, that not every one of these layers is necessarily required. These layers can also be incorporated using the formulations according to the invention, as defined above.

[0121] Preferably, one or more layers of an electronic device according to the invention are produced from a gas phase, preferably by resublimation. Accordingly, the granules present can preferably be designed such that the corresponding coating device can be fed with the granules.

[0122] In particular, it may be provided that the granules are transferred to an evaporation device.

[0123] Furthermore, it can be provided that one or more layers of an electronic device according to the invention are produced from a solution, e.g. by spin coating, or with any printing process, e.g. screen printing, flexographic printing or offset printing, but particularly preferably LITI (Light Induced Thermal Imaging, thermal transfer printing) or ink-jet printing.

[0124] The device is structured, contacted, and finally hermetically sealed in a manner known per se, depending on the application, since the service life of such devices is drastically reduced in the presence of water and / or air.

[0125] The granules according to the invention, the electronic devices obtainable therefrom, in particular organic electroluminescent devices, are characterized by one or more of the following surprising advantages over the prior art: 1. The granules according to the invention are characterized by high environmental friendliness, with a particularly high level of workplace safety. 2. The granules of the present invention can be produced cost-effectively. 3. The granules according to the invention enable the safe and reliable transport of compositions that can also be used for the production of very finely structured electronic devices. 4. The granules according to the invention can be processed with conventional equipment, thus also achieving cost advantages. 5.The electronic devices obtainable with the granules according to the invention exhibit very high stability, a very long service life, and excellent quality compared to electronic devices obtained with conventional solids, whereby these properties can also be achieved after a longer storage or transport period of the materials.

[0126] These aforementioned advantages do not come at the expense of other electronic properties.

[0127] It should be noted that variations of the embodiments described in the present invention fall within the scope of this invention. Unless explicitly excluded, each feature disclosed in the present invention may be replaced by alternative features serving the same, an equivalent, or a similar purpose. Thus, unless otherwise stated, each feature disclosed in the present invention is to be considered as an example of a generic series or as an equivalent or similar feature.

[0128] All features of the present invention can be combined with one another in any way, unless certain features and / or steps are mutually exclusive. This applies in particular to preferred features of the present invention. Likewise, features of non-essential combinations can be used separately (and not in combination).

[0129] It should also be noted that many of the features, and in particular those of the preferred embodiments of the present invention, are themselves inventive and not merely to be regarded as part of the embodiments of the present invention.

[0130] The teaching on technical action disclosed in the present invention can be abstracted and combined with other examples. A person skilled in the art can, from the descriptions, produce further electronic devices according to the invention without any inventive effort and thus implement the invention in its entire claimed scope.

[0131] The following schematic drawing illustrates the implementation of a method according to the invention using a system. Figures:

[0132] Figure 1Figure 1 shows a schematic representation of a system (1) for carrying out a process according to the invention. In the system (1), a melt of a functional material is supplied by a unit (10), also called a feed vessel, for the purpose of providing the melt. This unit is preferably designed as a system for the production of a functional material. The melt is directed from the unit (10) via a nozzle (14) into a downpipe (16). In the downpipe (16), the melt is cooled to form granules, which can then be removed from the downpipe. Optionally, further components can be included in the system setup; for example, a line (12) can be provided between the unit (10) and the nozzle (14). Furthermore, a line (18) can be provided from the downpipe (16) for discharging the granules. The system preferably also includes a collection vessel (19), which can also be connected directly to the downpipe without a line (18).. Figure 2 Figure 1 shows the functional material M-1 produced according to the inventive method. The average diameter of the granules is 0.94 mm.

[0133] It is obvious to those skilled in the art that many of the embodiments described above require additional components that are not explicitly detailed in the description of the system. These include, in particular, pumps, cooling units, and supply or discharge lines for the inert gases described above. Furthermore, it should be noted that the downpipe can be designed with components or structural features such that the formed components can be removed particularly easily and efficiently. Examples

[0134] M-1 were melted in the feed vessel (10) at 290°C and 500 mbar. The molten material flows through a nozzle (14) into the downpipe (16). The nozzle (14) has a diameter of 0.3 mm. The 2.5 m long downpipe (16) is filled with helium at a pressure of 335 mbar. The downpipe (16) is equipped with a cooling jacket over a length of 1.0 m, which is cooled with liquid nitrogen. The granules are collected in a receiving vessel (19).

[0135] There are no scaling limitations in continuous process operation. In batch operation, the processable quantities are determined by the volume of the feed vessel (10) and the collection vessel (19). Example 5 is not part of the present invention. Example. material feed vessel nozzle downpipe T [°C] p [mbar] d [mm] Total | [m] Cool | [m] T [°C] p [mbar] 1 M-1 290 500 0,3 2,5 1,0 -196 335 2 M-1 290 500 0,3 4,0 2,5 -80 335 3 M-2 280 500 0,3 2,5 1,0 -196 335 4 M-3 275 500 0,3 2,5 1,0 -196 335 5 M-4 60 700 0,21 8 6,5 -196 600

[0136] Figure 1shows the structure of a plant for the production of the granules. Figure 2 Figure 1 shows a granulate containing the functional material M-1 produced according to the inventive method. The average diameter of the granulate particles is 0.94 mm. It is clearly evident that the granulate contains little fines and little dust.

Claims

1. Process for the preparation of a granular material comprising at least one functional material (FM) which can be employed for the production of functional layers of electronic devices, comprising the steps of: A) provision of a melt of a functional material which can be employed for the production of functional layers of electronic devices, in a feed vessel; B) transfer of the melt obtained under A) into a drop tube; C) cooling of the melt transferred into the drop tube in step B) to give a granular material, characterised in that the pressure at which the melt is transferred into a drop tube in step B) is higher than the pressure in the drop tube, where the pressure in the feed vessel is in the range from 400 to 700 mbar and the absolute pressure in the drop tube is in the range from 250 to 500 mbar, in that the melt transferred into the drop tube in step B) is cooled in step C) using an inert gas, and in that the granular material obtained in step C) has a fines content, formed by particles having a diameter of less than 0.1 mm, of less than 0.1% by weight.

2. Process according to Claim 1, where the functional material (FM) which can be employed for the production of functional layers of electronic devices is selected from the group consisting of fluorescent emitters, phosphorescent emitters, emitters which exhibit TADF (thermally activated delayed fluorescence), host materials, electron-transport materials, exciton-blocking materials, electron-injection materials, holeconduction materials, hole-injection materials, n-dopants, p-dopants, wide band gap materials, electron-blocking materials, hole-blocking materials and / or materials which have liquid-crystalline properties.

3. Process according to Claim 1 or 2, where the functional material (FM) which can be employed for the production of functional layers of electronic devices can be melted without decomposition above a temperature of 50°C.

4. Process according to Claim 3, where the functional material (FM) which can be employed for the production of functional layers of electronic devices exhibits a degradation of at most 0.1% by weight over a storage duration of 10 hours in the molten state at the processing temperature.

5. Process according to Claim 1, where the inert gas has a temperature of at most 0°C, preferably in the range from -200 to -70°C.

6. Process according to one of the preceding claims, where the melt transferred into the drop tube in step B) is cooled in step C) over a drop height of at least 50 cm, preferably over a drop height in the range from 100 to 800 cm.

7. Process according to one of the preceding claims, where the melt is transferred into the drop tube in step B) through a nozzle.

8. Process according to Claim 7, where the nozzle has a diameter of at most 0.7 mm, preferably a diameter in the range from 0.1 to 0.5 mm, particularly preferably a diameter in the range from 0.2 to 0.3 mm.

9. Process according to one of the preceding claims, where the functional material (FM) which can be employed for the production of functional layers of electronic devices is selected from the group consisting of the group of the phenyls, fluorenes, indenofluorenes, spirobifluorenes, carbazoles, indenocarbazoles, indolocarbazoles, spirocarbazoles, pyrimidines, triazines, lactams, triarylamines, dibenzofurans, dibenzothienes, imidazoles, benzimidazoles, benzoxazoles, benzothiazoles, 5-aryl-phenanthridin-6-ones, 9,10-dehydrophenanthrenes, fluoranthenes, anthracenes, benzanthracenes, fluoradenes.

10. Granular material obtainable by a process of Claims 1 to 9, where the granular material has a fines content, formed by particles having a diameter of less than 0.1 mm, of less than 0.1% by weight.

11. Use of a granular material according to Claim 10 for the production of an electronic device.

12. Use according to Claim 11, where the granular material is transferred into an evaporator device.