Electronic device

Abstract

To provide an electronic device with improved performance data, particularly in terms of lifetime, efficiency, operating voltage and color purity.SOLUTION: The present application relates to an electronic device including, in this order, an anode, a hole injection layer, a hole transport layer, a light emitting layer, and a cathode. The hole transport layer contains a first compound selected from spirobifluorene amine and fluorene amine compounds, and a second compound different from the first compound and selected from spirobifluorene amine and fluorene amine compounds.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present application relates to an electronic device comprising, in that order, an anode, a hole injection layer, a hole transport layer, a light emitting layer, and a cathode. The hole transport layer contains a first compound selected from spirobifluorene amine and fluorene amine compounds, and a second compound different from the first compound and selected from spirobifluorene amine and fluorene amine compounds.

[0002] Electronic devices in the context of this application are understood to mean so-called organic electronic devices that contain organic semiconductor materials as functional materials. More specifically, they are understood to mean OLEDs (organic light-emitting diodes, organic electroluminescent devices). These are electronic devices that have one or more layers that contain organic compounds and emit light when a voltage is applied. The general principles of the construction and function of OLEDs are known to those skilled in the art.

[0003] A hole-injection layer is understood to mean a layer which assists the injection of holes from the anode of the OLED into the hole-transporting layer during operation of the electronic device. The hole-injection layer is preferably directly adjacent to the anode, with one or more hole-transporting layers being present on the cathode side directly adjacent to the hole-injection layer.

[0004] A hole-transporting layer is understood to be a layer capable of transporting holes during operation of an electronic device, more particularly, in an OLED, a layer disposed between the anode and the light-emitting layer closest to the anode.

[0005] In electronic devices, and in particular in OLEDs, there is a strong interest in improving performance data, especially lifetime, efficiency, operating voltage and color purity, aspects which still do not provide any completely satisfactory solutions.

[0006] The hole transporting layer has a significant influence on the above performance data of the electronic device. They may be present as a separate hole transporting layer between the anode and the light emitting layer, or in the form of multiple hole transporting layers, for example, two or three hole transporting layers, between the anode and the light emitting layer.

[0007] The materials for hole transporting layer known in the prior art are mainly amine compounds, especially triarylamine compounds.Examples of such triarylamine compounds are spirobifluoreneamine, fluoreneamine, indenofluoreneamine, phenanthreneamine, carbazoleamine, xantheneamine, spirodihydroacridineamine, biphenylamine and the combination of these structural elements with one or more amino groups, this is only a list, and those skilled in the art will recognize other structural classes.

[0008] It has now been discovered that an electronic device that contains an anode, a hole injection layer, a hole transport layer, a light emitting layer, and a cathode in this order, and the hole transport layer contains a first compound selected from spirobifluoreneamine and fluoreneamine compounds, and a second compound different from the first compound selected from spirobifluoreneamine and fluoreneamine compounds, has better performance data than prior art electronic devices in which the hole transport layer is formed from a single compound.More specifically, the lifetime and / or efficiency of such devices are improved compared to the above prior art devices.

[0009] Therefore, the present application: 1. An electronic device comprising: -anode, - cathode, a light-emitting layer disposed between the anode and the cathode; a hole injection layer disposed between the anode and the light-emitting layer; - disposed between the hole injection layer and the light-emitting layer and directly adjacent to the light-emitting layer on the anode side, and having the formulas (I) and (II)

[0010] [ka]

[0011] (In the ceremony Z is the same or different in each occurrence, CR 1 and N, where Z is

[0012] [ka]

[0013] If a group is attached thereto, it is C; X is the same or different in each occurrence and is a single bond, O, S, C(R 1 ) 2 and N.R. 1 Selected from; Ar 1 and Ar 2 are the same or different in each occurrence, have 6 to 40 aromatic ring atoms, and are one or more R 2 Aromatic ring systems substituted with radicals and having 5 to 40 aromatic ring atoms and one or more R 2 a heteroaromatic ring system substituted by a radical; R 1 and R 2 are the same or different in each case and are H, D, F, Cl, Br, I, C(=O)R 3 , CN, Si(R 3 ) 3 , N(R 3 ) 2 , P(=O)(R 3 ) 2 , OR 3 , S(=O)R 3 , S(=O) 2 R 3, a linear alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; 1 or R 2 The radicals may be linked to each other or may form a ring; the mentioned alkyl, alkoxy, alkenyl and alkynyl groups, as well as the mentioned aromatic and heteroaromatic ring systems, are each R 3 and one or more CH 2 The group is -R 3 C=CR 3 -, -C≡C-, Si(R 3 ) 2 , C=O, C=NR 3 , -C(=O)O-, -C(=O)NR 3 -, NR 3 , P(=O)(R 3 ), -O-, -S-, SO or SO 2 may be replaced by; R 3 are the same or different and are selected from H, D, F, Cl, Br, I, CN, an alkyl or alkoxy group having 1 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; two or more R 3 The radicals may be bonded to each other or may form a ring; the alkyl, alkoxy, alkenyl and alkynyl groups, aromatic and heteroaromatic ring systems mentioned may be substituted by one or more radicals selected from F and CN; n is 0, 1, 2, 3 or 4, and when n=0, Ar 1 There are no groups present and the nitrogen atom is directly attached to the remainder of the formula. A hole transport layer comprising two different compounds conforming to the same or different formulas selected from The present invention provides an electronic device comprising:

[0014] When n=2, two Ar 1 The group is -Ar 1 -Ar 1 - in a row. When n=3, three Ar 1 The group is -Ar 1 -Ar 1 -Ar 1 - in a row. When n=4, four Ar 1 The group is -Ar 1 -Ar 1 -Ar 1 -Ar 1 - are connected in a row in a continuous manner.

[0015] The following definitions are applicable to chemical groups used in this application. They are applicable unless any further specific definition is given.

[0016] An aryl group in the context of the present invention is understood to mean either a single aromatic ring, i.e. benzene, or a condensed aromatic polycycle, such as naphthalene, phenanthrene or anthracene. A condensed aromatic polycycle in the context of the present application consists of two or more single aromatic rings condensed together. Fusion between rings is understood here to mean that the rings share at least one edge with each other. An aryl group in the context of the present invention contains 6 to 40 aromatic ring atoms. In addition, an aryl group does not contain any heteroatoms as aromatic ring atoms.

[0017] A heteroaryl group in the context of the present invention is understood to mean either a single heteroaromatic ring, such as pyridine, pyrimidine or thiophene, or a fused heteroaromatic polycycle, such as quinoline or carbazole. A fused heteroaromatic polycycle in the context of the present application consists of two or more single aromatic or heteroaromatic rings fused together, at least one of the aromatic and heteroaromatic rings being a heteroaromatic ring. Fusion between rings is understood here to mean that the rings share at least one edge with each other. A heteroaryl group in the context of the present invention contains 5 to 40 aromatic ring atoms, at least one of which is a heteroatom. The heteroatoms of the heteroaryl group are preferably selected from N, O and S.

[0018] The aryl or heteroaryl groups, each of which may be substituted by the abovementioned radicals, are especially preferred: benzene, naphthalene, anthracene, phenanthrene, pyrene, dihydropyrene, chrysene, perylene, triphenylene, fluoranthene, benzoanthracene, benzophenanthrene, tetracene, pentacene, benzopyrene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indophenylene, ... , isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, benzimidazolo[1,2-a]benzimidazole, naphthoimidazole, phenanthroimidazole, pyridoimidazole, pyrazineimidazole, quinoxalineimidazole, oxazole, benzimidazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, pyrazine, phenazine, naphthyridine, azacarbazole, benzocarboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole This is understood to mean the radicals derived from 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine and benzothiadiazole.

[0019] An aromatic ring system in the context of the present invention is a system that does not necessarily contain only aryl groups, but may additionally contain one or more non-aromatic rings fused to at least one aryl group. These non-aromatic rings contain only carbon atoms as ring atoms. Examples of groups encompassed by this definition are tetrahydronaphthalene, fluorene and spirobifluorene. In addition, the term "aromatic ring system" includes systems consisting of two or more aromatic ring systems bonded to each other via single bonds, such as biphenyl, terphenyl, 7-phenyl-2-fluorenyl, quaterphenyl and 3,5-diphenyl-1-phenyl. An aromatic ring system in the context of the present invention contains 6 to 40 carbon atoms in the ring system, but does not contain heteroatoms. The definition of "aromatic ring system" does not include heteroaryl groups.

[0020] Heteroaromatic ring systems meet the above definition of aromatic ring systems, except that they must contain at least one heteroatom as a ring atom. As in the case of aromatic ring systems, heteroaromatic ring systems need not contain only aryl and heteroaryl groups, but may additionally contain one or more non-aromatic rings fused to at least one aryl or heteroaryl group. The non-aromatic ring may contain only carbon atoms as ring atoms, or may additionally contain one or more heteroatoms, the heteroatoms being preferably selected from N, O and S. An example of such a heteroaromatic ring system is benzopyranyl. In addition, the term "heteroaromatic ring system" is understood to mean a system consisting of two or more aromatic or heteroaromatic ring systems bonded to each other via single bonds, for example 4,6-diphenyl-2-triazinyl. Heteroaromatic ring systems in the context of the present invention contain 5 to 40 ring atoms selected from carbon and heteroatoms, at least one of the ring atoms being a heteroatom. The heteroatoms of the heteroaromatic ring system are preferably selected from N, O and S.

[0021] Thus, the terms "heteroaromatic ring system" and "aromatic ring system" as defined herein differ from each other in that an aromatic ring system cannot have a heteroatom as a ring atom, while a heteroaromatic ring system must have at least one heteroatom as a ring atom, which may be present as a ring atom of a non-aromatic or aromatic heterocyclic ring.

[0022] According to the above definitions, any aryl group is encompassed by the term "aromatic ring system" and any heteroaryl group is encompassed by the term "heteroaromatic ring system".

[0023] An aromatic ring system having 6 to 40 aromatic ring atoms or a heteroaromatic ring system having 5 to 40 aromatic ring atoms is understood to mean, in particular, radicals derived from the radicals mentioned above under the aryl and heteroaryl radicals, and from biphenyl, terphenyl, quaterphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, indenofluorene, truxene, isotruxene, spirotruxene, spiroisotruxene, indenocarbazole, or a combination of these radicals.

[0024] In the context of the present invention, linear alkyl groups having 1 to 20 carbon atoms and branched or cyclic alkyl groups having 3 to 20 carbon atoms and alkenyl or alkynyl groups having 2 to 40 carbon atoms are each independently selected from the group consisting of individual hydrogen atoms or CH 2The radicals may also be substituted by the radicals mentioned above in the definition of the radicals, preferably the methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl or octynyl radicals.

[0025] An alkoxy or thioalkyl group having 1 to 20 carbon atoms is substituted with individual hydrogen atoms or CH 2The radicals may also be replaced by the radicals mentioned above in the definition of the radicals, preferably methoxy, trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, s-pentoxy, 2-methylbutoxy, n-hexoxy, cyclohexyloxy, n-heptoxy, cycloheptyloxy, n-octyloxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy, 2,2,2-trifluoroethoxy, methylthio, ethylthio, n-propylthio, i-propylthio, n-butylthio, i-butylthio, s-butylthio, t-butylthio. , n-pentylthio, s-pentylthio, n-hexylthio, cyclohexylthio, n-heptylthio, cycloheptylthio, n-octylthio, cyclooctylthio, 2-ethylhexylthio, trifluoromethylthio, pentafluoroethylthio, 2,2,2-trifluoroethylthio, ethenylthio, propenylthio, butenylthio, pentenylthio, cyclopentenylthio, hexenylthio, cyclohexenylthio, heptenylthio, cycloheptenylthio, octenylthio, cyclooctenylthio, ethynylthio, propynylthio, butynylthio, pentynylthio, hexynylthio, heptynylthio or octynylthio.

[0026] The expression that two or more radicals may together form a ring is to be understood in the context of this application as meaning, inter alia, that the two radicals are bonded to each other by a chemical bond, but in addition, the above expression should also be understood as meaning that if one of the two radicals is hydrogen, the second radical is bonded to the position where the hydrogen atom was bonded to form a ring.

[0027] The electronic device is preferably an organic electroluminescent device (OLED).

[0028] Preferred anodes for electronic devices are materials with a high work function. Preferably, the anode has a work function of more than 4.5 eV vs. vacuum. Firstly, metals with high redox potentials are suitable for this purpose, such as Ag, Pt or Au. Secondly, metal / metal oxide electrodes (e.g. Al / Ni / NiO x , Al / PtO x ) may be preferred. Depending on the application, at least one of the electrodes should be transparent or partially transparent to allow either irradiation of the organic material (organic solar cells) or emission of light (OLED, O-laser). Preferred anode materials in this case are conductive mixed metal oxides. Indium tin oxide (ITO) or indium zinc oxide (IZO) are particularly preferred. Furthermore, conductive doped organic materials, especially conductive doped polymers, are preferred. In addition, the anode may also consist of two or more layers, for example an inner layer of ITO and an outer layer of a metal oxide, preferably tungsten oxide, molybdenum oxide or vanadium oxide.

[0029] Preferred cathodes for electronic devices are metals, metal alloys or multilayer structures made up of different metals, such as alkaline earth metals, alkali metals, main group metals or lanthanides (e.g. Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.) with a low work function. Also suitable are alloys made up of alkali metals or alkaline earth metals and silver, such as alloys made up of magnesium and silver. In the case of multilayer structures, in addition to the metals mentioned, it is also possible to use further metals with a relatively high work function, such as Ag or Al, in which case metal combinations such as Ca / Ag, Mg / Ag or Ba / Ag are commonly used. It may also be preferable to introduce a thin intermediate layer of a material with a high dielectric constant between the metallic cathode and the organic semiconductor. Examples of materials useful for this purpose are alkali metal or alkaline earth metal fluorides as well as the corresponding oxides or carbonates (e.g. LiF, Li 2 O, BaF 2 , MgO, NaF, CsF, Cs 2 CO 3For this purpose, it is also possible to use lithium quinolinate (LiQ). The layer thickness of this layer is preferably 0.5 to 5 nm.

[0030] The light-emitting layer of the device may be a fluorescent or phosphorescent light-emitting layer. The light-emitting layer of the device is preferably a fluorescent light-emitting layer, particularly preferably a blue fluorescent light-emitting layer. In the fluorescent light-emitting layer, the emitter is preferably a singlet emitter, i.e. a compound that emits light from an excited singlet state when the device is operated. In the phosphorescent light-emitting layer, the emitter is preferably a triplet emitter, i.e. a compound that emits light from an excited triplet state or from a state with a higher spin quantum number, such as a quintet state, when the device is operated.

[0031] In a preferred embodiment, the fluorescent light-emitting layer used is a blue-fluorescent layer.

[0032] In a preferred embodiment, the phosphorescent light-emitting layer used is a green or red phosphorescent light-emitting layer.

[0033] Suitable phosphorescent emitters are especially compounds which, when appropriately excited, preferably emit light in the visible range and which also contain at least one atom with an atomic number greater than 20, preferably greater than 38 and less than 84, more preferably greater than 56 and less than 80. As phosphorescent emitters it is preferred to use compounds which contain copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, especially compounds which contain iridium, platinum or copper.

[0034] In general, all phosphorescent complexes as used in phosphorescent OLEDs according to the prior art and known to those skilled in the art of organic electroluminescent devices are suitable for use in the device of the present invention.

[0035] Preferred compounds for use as phosphorescent emitters are shown in the table below:

[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

change

[0042]

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[0043]

change

[0044]

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[0045]

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[0046]

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[0047] Preferred fluorescent compounds are selected from the class of arylamines. Arylamines or aromatic amines in the context of the present invention are understood to mean compounds containing three substituted or unsubstituted aromatic or heteroaromatic ring systems directly bonded to the nitrogen. Preferably, at least one of these aromatic or heteroaromatic ring systems is a fused ring system, more preferably having at least 14 aromatic ring atoms. Preferred examples of these are aromatic anthracenamines, aromatic anthracenediamines, aromatic pyrenamines, aromatic pyrenediamines, aromatic chrysenamines or aromatic chrysenediamines. Aromatic anthracenamines are understood to mean compounds in which a diarylamino group is directly bonded to an anthracene group, preferably in the 9-position. Aromatic anthracenediamines are understood to mean compounds in which two diarylamino groups are directly bonded to an anthracene group, preferably in the 9- and 10-positions. Aromatic pyrenamines, pyrenediamines, chrysenamines and chrysenediamines are similarly defined, with the diarylamino group being bonded to the pyrene, preferably in the 1- or 1- and 6-positions. Further preferred luminescent compounds are indenofluorene amines or diamines, benzoindenofluorene amines or diamines, and dibenzoindenofluorene amines or diamines, as well as indenofluorene derivatives with condensed aryl groups.Also preferred are pyrene arylamines.Also preferred are benzoindenofluorene amines, benzofluorene amines, extended benzoindenofluorenes, phenoxazines, and fluorene derivatives that are linked to furan or thiophene units.

[0048] Preferred compounds for use as fluorescent emitters are shown in the table below:

[0049] [ka]

[0050] [ka]

[0051] [ka]

[0052] [ka]

[0053] [ka]

[0054] [ka]

[0055] [ka]

[0056] [ka]

[0057] [ka]

[0058] In a preferred embodiment, the light-emitting layer of the electronic device contains exactly one matrix compound. Matrix compound is understood to mean a compound that is not a light-emitting compound. This embodiment is particularly preferred in the case of a fluorescent light-emitting layer.

[0059] In an alternative preferred embodiment, the light-emitting layer of the electronic device contains exactly two or more, preferably exactly two, matrix compounds. This embodiment is also referred to as a mixed matrix system and is particularly preferred in the case of phosphorescent light-emitting layers.

[0060] In the case of the phosphorescent light-emitting layer, the total proportion of all matrix materials is preferably between 50.0% and 99.9%, more preferably between 80.0% and 99.5%, and most preferably between 85.0% and 97.0%.

[0061] Figures relating to proportions in % are understood here to mean proportions in % by volume in the case of layers which are applied from the gas phase and proportions in % by weight in the case of layers which are applied from solution.

[0062] Correspondingly, the proportion of phosphorescent compounds is preferably 0.1% to 50.0%, more preferably 0.5% to 20.0%, and most preferably 3.0% to 15.0%.

[0063] For the fluorescent-emitting layer, the total percentage of all matrix materials is preferably between 50.0% and 99.9%, more preferably between 80.0% and 99.5%, and most preferably between 90.0% and 99.0%.

[0064] Correspondingly, the proportion of the fluorescent compound is between 0.1% and 50.0%, preferably between 0.5% and 20.0%, and more preferably between 1.0% and 10.0%.

[0065] The mixed matrix system preferably comprises two or three different matrix materials, more preferably two different matrix materials. Preferably, in this case, one of the two materials is a material with properties including hole transport properties and the other material is a material with properties including electron transport properties. Further matrix materials that may be present in the mixed matrix system are compounds with a large energy difference between HOMO and LUMO (wide band gap materials). The two different matrix materials may be present in a ratio of 1:50 to 1:1, preferably 1:20 to 1:1, more preferably 1:10 to 1:1, most preferably 1:4 to 1:1. For phosphorescent organic electroluminescent devices, it is preferred to use a mixed matrix system.

[0066] Preferred matrix materials for fluorescent light-emitting compounds are selected from the classes of oligoarylenes (e.g. 2,2',7,7'-tetraphenylspirobifluorene), especially oligoarylenes containing fused aromatic groups, oligoarylenevinylenes, polypodal metal complexes, hole-conducting compounds, electron-conducting compounds, especially ketones, phosphine oxides and sulfoxides; atropisomers, boronic acid derivatives, and benzanthracenes. Particularly preferred matrix materials are selected from the classes of oligoarylenes containing naphthalene, anthracene, benzanthracene, and / or pyrene or atropisomers of these compounds, oligoarylenevinylenes, ketones, phosphine oxides, and sulfoxides. Very particularly preferred matrix materials are selected from the classes of oligoarylenes containing anthracene, benzanthracene, benzophenanthrene, and / or pyrene or atropisomers of these compounds. An oligoarylene in the context of this invention is of course understood to mean a compound in which at least three aryl or arylene groups are linked together.

[0067] Preferred matrix materials for the fluorescent compounds are shown in the table below:

[0068] [ka]

[0069] [ka]

[0070] [ka]

[0071] [ka]

[0072] Preferred matrix materials for phosphorescent emitters are aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones, triarylamines, carbazole derivatives such as CBP (N,N-biscarbazolylbiphenyl), indolocarbazole derivatives, indenocarbazole derivatives, azacarbazole derivatives, bipolar matrix materials, silanes, azaboroles or boronic esters, triazine derivatives, zinc complexes, diazasiloles or tetraazasilol derivatives, diazaphosphole derivatives, bridged carbazole derivatives, triphenylene derivatives, or lactams.

[0073] In preferred embodiments, the electronic device contains exactly one light-emitting layer.

[0074] In an alternative preferred embodiment, the electronic device contains multiple light-emitting layers, preferably two, three or four light-emitting layers. This is especially preferred for white light-emitting electronic devices.

[0075] More preferably, the light-emitting layer in this case has several emission maxima in total between 380 nm and 750 nm, such that the electronic device emits white light; in other words, various light-emitting compounds that can fluoresce or phosphoresce and emit blue, green, yellow, orange or red light are used in the light-emitting layer. Particularly preferred are three-layer systems, i.e. systems with three light-emitting layers, one of the three layers in each case exhibiting blue emission, one of the three layers in each case exhibiting green emission and one of the three layers in each case exhibiting orange or red emission. For the production of white light, it may be possible to use individual light-emitting compounds that emit over a wide wavelength range, rather than multiple light-emitting compounds that emit colored light.

[0076] In a preferred embodiment of the invention, the electronic device comprises two or three, preferably three, identical or different layer sequences stacked on top of one another, each of the layer sequences comprising the following layers: a hole injection layer, a hole transport layer, an electron blocking layer, an emissive layer, and an electron transport layer, at least one, preferably all, of the layer sequences being The following layers: a hole injection layer disposed between the anode and the light-emitting layer; a hole-transporting layer disposed between the hole-injection layer and the light-emitting layer and directly adjacent to the light-emitting layer on the anode side, the hole-transporting layer containing two different compounds conforming to the same or different formulas selected from formulas (I) and (II); Contains:

[0077] A double layer consisting of adjacent n-CGL and p-CGL is preferably arranged in each case between the layer sequences, the n-CGL being arranged on the anode side and the p-CGL being arranged correspondingly on the cathode side. Here, CGL stands for charge generating layer. The materials used for such layers are known to those skilled in the art. It is preferable to use p-doped amines for the p-CGL, more preferably materials selected from the preferred structural classes of hole transport materials mentioned below.

[0078] The hole transport layer preferably has a thickness of 20 nm to 300 nm, more preferably 30 nm to 250 nm, and further preferably has a thickness of 250 nm or less.

[0079] Preferably, the hole transporting layer contains exactly two, three or four, preferably exactly two or three, most preferably exactly two different compounds conforming to the same or different formulas selected from formulas (I) and (II).

[0080] Preferably, the hole transporting layer consists of compounds conforming to the same or different formulas selected from formulas (I) and (II). "Consisting of" is understood here to mean that no further compounds are present in the layer, except for trace amounts of impurities that typically occur as further compounds in the layer in the manufacturing process of an OLED.

[0081] In an alternative preferred embodiment, the hole transporting layer contains a p-dopant in addition to a compound conforming to the same or a different formula selected from formulas (I) and (II).

[0082] The p-dopants used in accordance with the present invention are preferably organic electron acceptor compounds capable of oxidizing one or more other compounds in the mixture.

[0083] Particularly preferred p-dopants are quinodimethane compounds, azaindenofluorenediones, azaphenalenes, azatriphenylenes, I 2 , metal halides, preferably transition metal halides, metal oxides, preferably metal oxides containing at least one transition metal or metal of the third main group, and transition metal complexes, preferably complexes of Cu, Co, Ni, Pd and Pt with ligands containing at least one oxygen atom as binding site. As dopants further transition metal oxides are preferred, preferably oxides of rhenium, molybdenum and tungsten, more preferably oxides of Re. 2 O 7 , MoO 3 , WO 3 and ReO 3 Even more preferred are complexes of bismuth in the (III) oxidation state, more particularly bismuth(III) complexes having electron-deficient ligands, more particularly carboxylate ligands.

[0084] The p-dopant is preferably substantially uniformly distributed in the p-doped layer. This can be achieved, for example, by co-evaporation of the p-dopant with the hole transport material matrix. The p-dopant is preferably present in the p-doped layer in a proportion of 1% to 10%.

[0085] Preferred p-dopants are especially the following compounds:

[0086] [ka]

[0087] In a preferred embodiment of the invention, the hole transporting layer contains two different compounds conforming to formula (I).

[0088] Two different compounds conforming to the same or different formulas selected from formulas (I) and (II) are preferably present in the hole transport layer in a proportion of at least 5% each. They are more preferably present in a proportion of at least 10%. It is preferred that one of the compounds is present in a higher proportion than the other compound, more preferably in a proportion 2 to 5 times higher than the proportion of the other compound. This is especially true when the hole transport layer contains exactly two compounds conforming to the same or different formulas selected from formulas (I) and (II). Preferably, for one of the compounds, the proportion in the layer is 15% to 35%, and for the other of the two compounds, the proportion in the layer is 65% to 85%.

[0089] Of formulas (I) and (II), formula (I) is preferred.

[0090] Formulae (I) and / or (II) must comply with one or more, preferably all, of the following preferences: In a preferred embodiment, the compound has a single amino group.Amino group is understood to mean a group that has a nitrogen atom with three binding partners.It is understood to mean a group that has three groups that are preferably selected from aromatic and heteroaromatic groups that are bound to the nitrogen atom.

[0091] In an alternative preferred embodiment, the compound has exactly two amino groups.

[0092] Z is preferably CR 1 where Z is

[0093] [ka]

[0094] If a group is attached thereto, it is C; X is preferably a single bond; Ar 1 are preferably the same or different in each occurrence and selected from divalent radicals derived from benzene, biphenyl, terphenyl, naphthalene, fluorene, indenofluorene, indenocarbazole, spirobifluorene, dibenzofuran, dibenzothiophene, and carbazole, each of which may be selected from one or more R 2 Most preferably, the radical is Ar 1 are the same or different in each occurrence and in each occurrence one or more R 2 It is a divalent group derived from benzene substituted with the Ar radical. 1 The groups may be the same or different in each case.

[0095] The index n is preferably 0, 1 or 2, more preferably 0 or 1, and most preferably 0.

[0096] When n=1, the preferred -(Ar 1 ) n The - group has the formula:

[0097] [ka]

[0098] [ka]

[0099] [ka]

[0100] [ka]

[0101] [ka]

[0102] [ka]

[0103] (wherein the dotted line represents the bond to the remainder of the formula, and the groups at the positions shown as unsubstituted are each R 2 are substituted by radicals, and R 2 The radical is preferably H. Matches

[0104] Ar 2 The radicals are preferably in each case the same or different and are selected from monovalent radicals derived from benzene, biphenyl, terphenyl, quaterphenyl, naphthalene, fluorene, especially 9,9′-dimethylfluorene and 9,9′-diphenylfluorene, 9-silafluorene, especially 9,9′-dimethyl-9-silafluorene and 9,9′-diphenyl-9-silafluorene, benzofluorene, spirobifluorene, indenofluorene, indenocarbazole, dibenzofuran, dibenzothiophene, benzocarbazole, carbazole, benzofuran, benzothiophene, indole, quinoline, pyridine, pyrimidine, pyrazine, pyridazine and triazine, the monovalent radicals each being selected from one or more R 2 or Ar 2The radicals may in each case be the same or different and are preferably selected from a combination of radicals derived from benzene, biphenyl, terphenyl, quaterphenyl, naphthalene, fluorene, especially 9,9′-dimethylfluorene and 9,9′-diphenylfluorene, 9-silafluorene, especially 9,9′-dimethyl-9-silafluorene and 9,9′-diphenyl-9-silafluorene, benzofluorene, spirobifluorene, indenofluorene, indenocarbazole, dibenzofuran, dibenzothiophene, carbazole, benzofuran, benzothiophene, indole, quinoline, pyridine, pyrimidine, pyrazine, pyridazine and triazine, each of which may be selected from the group consisting of one or more R 2 It is substituted by a radical.

[0105] Particularly preferred is Ar 2 The radicals are in each case the same or different and are selected from phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, fluorenyl, especially 9,9′-dimethylfluorenyl and 9,9′-diphenylfluorenyl, benzofluorenyl, spirobifluorenyl, indenofluorenyl, indenocarbazolyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, benzofuranyl, benzothiophenyl, benzo-fused dibenzofuranyl, benzo-fused dibenzothiophenyl, naphthyl-substituted phenyl, fluorenyl-substituted phenyl, spirobifluorenyl-substituted phenyl, dibenzofuranyl-substituted phenyl, dibenzothiophenyl-substituted phenyl, carbazolyl-substituted phenyl, pyridyl-substituted phenyl, pyrimidyl-substituted phenyl and triazinyl-substituted phenyl, the mentioned radicals each being selected from the group consisting of one or more R 2 It is substituted by a radical.

[0106] Particularly preferred is Ar 2 The groups may be the same or different and have the formula:

[0107] [ka]

[0108]

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[0109]

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[0110]

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[0111]

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[0112]

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[0113]

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[0114]

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[0115]

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[0116]

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[0117]

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[0118]

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[0119] [ka]

[0120] [ka]

[0121] [ka]

[0122] [ka]

[0123] [ka]

[0124] [ka]

[0125] [ka]

[0126] (wherein the group at the position shown as unsubstituted is R 2 are substituted by radicals, and R 2 is preferably H, and the bond shown with a dotted line is the bond to the amine nitrogen atom. is selected from.

[0127] Preferably, R 1 and R 2 are the same or different in each case and are H, D, F, CN, Si(R 3 )3 , N(R 3 ) 2 , a linear alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; the mentioned alkyl and alkoxy groups, the mentioned aromatic ring systems, and the mentioned heteroaromatic ring systems are each selected from R 3 radical; one or more CH 2 The group is -C≡C-, R 3 C=CR 3 -, Si(R 3 ) 2 , C=O, C=NR 3 , -NR 3 -, -O-, -S-, -C(=O)O- or -C(=O)NR 3 - may be replaced by

[0128] More preferably, R 1 are in each occurrence the same or different and are selected from H, D, F, CN, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; the mentioned aromatic ring systems and the mentioned heteroaromatic ring systems are each represented by R 3 It is substituted by a radical.

[0129] More preferably, R 2 are the same or different in each case and are H, D, F, CN, Si(R 3 ) 4 , a linear alkyl group having 1 to 10 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms, the alkyl group mentioned, the aromatic ring system mentioned and the heteroaromatic ring system mentioned being each selected from R 3 It is substituted by a radical.

[0130] - Z is CR 1 where Z is

[0131] [ka]

[0132] If a group is attached thereto, it is C; - X is a single bond; - Ar 1 are the same or different in each occurrence and in each occurrence one or more R 2 is a divalent group derived from benzene substituted by a radical; - the subscript n is either 0 or 1; - Ar 2 are the same or different in each case and are represented by the above formula Ar 2 -1~Ar 2 - Selected from 272; - R 1 are in each occurrence the same or different and are selected from H, D, F, CN, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; the mentioned aromatic ring systems and the mentioned heteroaromatic ring systems are each represented by R 3 is substituted by a radical; - R 2 are the same or different in each case and are H, D, F, CN, Si(R 3 ) 4 , a linear alkyl group having 1 to 10 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms, the alkyl group mentioned, the aromatic ring system mentioned and the heteroaromatic ring system mentioned being each selected from R 3 Substituted by a radical It is particularly preferred.

[0133] Formula (I) is preferably represented by formula (I-1)

[0134] [ka]

[0135] in which the occurring groups are as defined above, preferably according to their preferred embodiments, and unoccupied positions on the spirobifluorene are R 1 substituted by a radical).

[0136] Formula (II) is preferably formula (II-1)

[0137] [ka]

[0138] in which the occurring groups are as defined above, preferably according to their preferred embodiments, and unoccupied positions on the fluorene are R 1 (substituted by radicals) Matches

[0139] Preferred embodiments of the compounds of formula (I) are those compounds cited as exemplary structures in WO2015 / 158411, WO2011 / 006574, WO2013 / 120577, WO2016 / 078738, WO2017 / 012687, WO2012 / 034627, WO2013 / 139431, WO2017 / 102063, WO2018 / 069167, WO2014 / 072017, WO2017 / 102064, WO2017 / 016632, WO2013 / 083216 and WO2017 / 133829.

[0140] Preferred embodiments of compounds of formula (II) are the compounds cited as exemplary structures in WO2014 / 015937, WO2014 / 015938, WO2014 / 015935 and WO2015 / 082056.

[0141] Hereinafter, one of the two different compounds in the hole transport layer that meet the same or different formula selected from formulas (I) and (II) will be referred to as HTM-1, and the other of the two different compounds in the hole transport layer that meet the same or different formula selected from formulas (I) and (II) will be referred to as HTM-2.

[0142] In a preferred embodiment, HTM-1 is represented by the formula (I-1-A) and (II-1-A):

[0143] [ka]

[0144] and HTM-2 is selected from the formulas (I-1-B), (I-1-C), (I-1-D), (II-1-B), (II-1-C), and (II-1-D).

[0145] [ka]

[0146] wherein the groups occurring in formulae (I-1-A) to (I-1-D) and (II-1-B) to (II-1-D) are as defined above, preferably according to their preferred embodiments, and the unoccupied positions on the spirobifluorene and fluorene are each selected from the group consisting of R 1 Radicals are substituted. More preferably, HTM-2 conforms to formula (I-1-B) or (I-1-D), most preferably formula (I-1-D). In alternative preferred embodiments, HTM-2 conforms to formula (II-1-B) or (II-1-D), most preferably formula (II-1-D).

[0147] Preferably, HTM-1 is present in the hole transporting layer in a proportion that is 5 to 2 times higher than the proportion of HTM-2 in the layer.

[0148] Preferably, HTM-1 is present in the layer in an amount of 50% to 95%, more preferably in an amount of 60% to 90%, and most preferably in an amount of 65% to 85%.

[0149] Preferably, HTM-2 is present in the layer in an amount of from 5% to 50%, more preferably from 10% to 40%, and most preferably from 15% to 35%.

[0150] Preferably, HTM-1 is present in the layer in a proportion of 65% to 85%, and HTM-2 is present in the layer in a proportion of 15% to 35%.

[0151] In a preferred embodiment, HTM-1 has a HOMO between -4.8 eV and -5.2 eV, and HTM-2 has a HOMO between -5.1 eV and -5.4 eV. More preferably, HTM-1 has a HOMO between -5.0 and -5.2 eV, and HTM-2 has a HOMO between -5.1 and -5.3 eV. It is even more preferred that HTM-1 has a higher HOMO than HTM-2. More preferably, HTM-1 has a HOMO between 0.02 and 0.3 eV higher than HTM-2. "Higher HOMO" is understood here to mean a less negative value in eV.

[0152] The HOMO energy level is determined by cyclic voltammetry (CV), ie by the method described in published specification WO2011 / 032624, page 28, line 1 to page 29, line 21.

[0153] Preferred embodiments of compound HTM-1 are shown in the table below:

[0154] [ka]

[0155] [ka]

[0156] Preferred embodiments of compound HTM-2 are shown in the table below:

[0157] [ka]

[0158] [ka]

[0159] [ka]

[0160] [ka]

[0161] [ka]

[0162] The hole injection layer of the electronic device is preferably directly adjacent to the anode. It is even more preferred that it is directly adjacent to the hole transport layer on the anode side. More preferably, the electronic device has a layer sequence of anode / hole injection layer / hole transport layer / light emitting layer, the mentioned layers being directly adjacent to each other.

[0163] The hole injection layer has a thickness of preferably 2 to 50 nm, more preferably 2 to 30 nm.The hole injection layer has a thickness of preferably 50 nm or less, more preferably 30 nm or less.

[0164] In a preferred embodiment, the hole injection layer contains a mixture of a p-dopant as described above and a hole transport material. The p-dopant is present in the hole injection layer here preferably in a proportion of 1% to 10%. Here, the hole transport material is preferably selected from the classes of materials known to the skilled in the art as hole transport materials for OLEDs, especially triarylamines. Particularly preferred are indenofluorene amine derivatives, amine derivatives, amine derivatives with condensed aromatic systems, monobenzoindenofluorene amines, dibenzoindenofluorene amines, spirobifluorene amines, fluorene amines, spirodibenzopyran amines, dihydroacridine derivatives, spirodibenzofurans and spirodibenzothiophenes, phenanthre diarylamines, spirotribenzotropolones, spirobifluorenes with metaphenyldiamine groups, spirobisacridines, xanthene diarylamines, as well as 9,10-dihydroanthracene spiro compounds with diarylamino groups.

[0165] Specific compounds preferred for use as hole transport materials in the hole injection layer are shown in the table below:

[0166] [ka]

[0167] [ka]

[0168] [ka]

[0169] [ka]

[0170] [ka]

[0171]

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[0172]

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[0173]

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[0174]

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[0175]

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[0176]

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[0177]

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[0178]

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[0179]

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[0180] The above compounds H-1 to H-146 are generally suitable for use not only in hole injection layers but also in layers having a hole transport function, such as hole injection layers, hole transport layers and / or electron blocking layers, or as matrix materials in light-emitting layers, in particular light-emitting layers containing one or more phosphorescent emitters.

[0181] Compounds H-1 to H-146 are generally well suited for use in the above-mentioned OLEDs of any design and composition, as well as in the OLEDs according to the present application. The compounds show good performance data in OLEDs, especially good lifetime and good efficiency.

[0182] The hole transport material of the hole injection layer is more preferably selected from spirobifluorenylamines and fluorenylamines, more preferably from spirobifluorenylmonoamines and fluorenylmonoamines. Here, monoamine is understood to mean a compound that contains a single amine group. Most preferably, the hole transport material of the hole injection layer is selected from the compounds of formula (I-1-A) and (II-1-A) defined above, more preferably from the compounds of formula (I-1-A).

[0183] In an alternative preferred embodiment, the hole injection layer contains a hexaazatriphenylene derivative, preferably as described in US2007 / 0092755, or another highly electron-deficient and / or Lewis acidic compound, in each case in pure form, i.e. not as a mixture with another compound. Examples of such compounds include bismuth complexes, especially Bi(III) complexes, especially Bi(III) carboxylates, such as compound D-13 above.

[0184] Besides the cathode, anode, light-emitting layer, hole-injection layer and hole-transporting layer, the electronic device preferably also contains further layers. These are preferably selected in each case from one or more hole-blocking layers, electron-transporting layers, electron-injecting layers, exciton-blocking layers, intermediate layers, charge-generating layers, and / or organic or inorganic p / n junctions. However, it should be pointed out that not all of these layers necessarily need to be present. More particularly, the electronic device preferably contains one or more layers selected from electron-transporting layers and electron-injecting layers arranged between the light-emitting layer and the anode. More preferably, the electronic device contains one or more electron-transporting layers, preferably a single electron-transporting layer, and a single electron-injecting layer, in this order, between the light-emitting layer and the cathode, and the mentioned electron-injecting layer is preferably directly adjacent to the cathode.

[0185] The arrangement of layers in the electronic device is preferably as follows: -anode- -Hole injection layer- -Hole transport layer- -Emitting layer- -Optional hole blocking layer- -Electron transport layer- -Electron injection layer- -Cathode-.

[0186] Suitable materials for hole blocking layers, electron transport layers and electron injection layers in electronic devices are, inter alia, aluminum complexes such as Alq 3 , zirconium complexes, such as Zrq 4 , lithium complexes such as Liq, benzimidazole derivatives, triazine derivatives, pyrimidine derivatives, pyridine derivatives, pyrazine derivatives, quinoxaline derivatives, quinoline derivatives, oxadiazole derivatives, aromatic ketones, lactams, boranes, diazaphosphole derivatives and phosphine oxide derivatives. Examples of specific compounds for use in these layers are given in the table below:

[0187] [ka]

[0188] [ka]

[0189] [ka]

[0190] In a preferred embodiment, the electronic device is characterized in that one or more layers are applied by sublimation. In this case, the material is applied in a vacuum sublimation system at 10 -5 Less than mbar, preferably less than 10 -6 It is applied by evaporation at an initial pressure of less than 10 mbar. However, in this case, the initial pressure can be lowered, for example to 10 -7 It is also possible to go below mbar.

[0191] Likewise preferred are electronic devices characterized in that one or more layers are applied by the OVPD (organic vapor phase deposition) method or with the aid of carrier gas sublimation. In this case, the material is preferably 10 -5 It is applied at a pressure of between mbar and 1 bar. A special case of this method is the OVJP (Organic Vapor Jet Printing) method, in which the material is applied directly by a nozzle and thus structured (eg MS Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

[0192] In addition, electronic devices are preferred, characterized in that one or more layers are produced from solution, for example by spin-coating, or by any printing method, such as screen printing, flexographic printing, nozzle printing or offset printing, but more preferably by LITI (Light Induced Thermal Imaging, Thermal Transfer Printing) or inkjet printing. For this purpose, soluble compounds are required. High solubility can be achieved by suitable substitution of the compounds.

[0193] More preferably, the electronic devices of the present invention are fabricated by applying one or more layers from solution and applying one or more layers by sublimation.

[0194] After application of the layers, the device is structured (depending on the application), the contacts are connected and finally sealed to eliminate the damaging effects of water and air.

[0195] The electronic device of the present invention is preferably used in a display, as a light source in lighting applications or as a light source in medical and / or cosmetic applications.

[0196] [example] 1) General manufacturing method of OLED and evaluation of OLED characteristics A glass plaque coated with a 50 nm thick structured ITO (indium tin oxide) is the substrate onto which the OLED is applied.

[0197] An OLED basically has the following layer structure: substrate / hole injection layer (HIL) / hole transport layer (HTL) / emissive layer (EML) / electron transport layer (ETL) / electron injection layer (EIL), and finally a cathode. The cathode is formed by a 100 nm thick layer of aluminum. The exact structure of the OLED can be found in Table 1.

[0198] All materials are applied by thermal evaporation in a vacuum chamber. Here, the emissive layer consists in this example of a matrix material (host material) and an emissive dopant (emitter) that is added to the matrix material in a certain volume percentage by co-evaporation. Details given in the form SMB1:SEB1(5%) here mean that the material SMB1 is present in the layer in a volume percentage of 95% and the material SEB1 in a volume percentage of 5%. Similarly, the electron transport layer and, in certain examples, the HIL and / or HTL also consist of a mixture of two materials, the material percentages being reported as specified above.

[0199] The chemical structures of the materials used in OLEDs are shown in Table 2.

[0200] The OLEDs are characterized by standard methods. For this purpose, the electroluminescence spectrum, the external quantum efficiency (EQE, measured in %) as a function of luminance calculated from the current-voltage-luminance characteristic assuming Lambertian emission characteristics, and the lifetime are determined. The parameter EQE@10 mA / cm 2 is 10mA / cm 2 The parameter U@10mA / cm 2 is 10mA / cm 2 The lifetime LT is defined as the time until the luminance drops to a certain percentage from the initial luminance during operation at a constant current density. The LT80 figure here means that the lifetime recorded corresponds to the time until the luminance drops to 80% of its initial value. @60mA / cm 2 The figure here indicates that the relevant lifetime is 60mA / cm 2 This means that the temperature is measured at

[0201] 2) OLEDs with a mixture of two different materials in the HTL with a p-doped HIL and a comparative example with a single material in the HTL We manufacture the following OLEDs:

[0202] [Table 1]

[0203] This gives the following measurement data:

[0204] [Table 2]

[0205] By adding compound HTM5 to the HTL containing HTM3, a clear efficiency increase is achieved at the same voltage in OLED I1, which is compared with OLED C1, which contains only compound HTM3 in the HTL and has the same structure.

[0206] A clear increase in efficiency is also found when the compound HTM6 is added to the HTL containing HTM2 (OLED I2), compared to the otherwise identically structured OLED C2, where the HTL contains only the compound HTM2.

[0207] Although the efficiency gains are small in percentage terms, they cannot be ignored since efficiency gains are difficult to achieve.

[0208] 3) An OLED with a HIL composed of a single material, the HTL containing a mixture of two different materials, and a comparative example with a single material in the HTL We manufacture the following OLEDs:

[0209] [Table 3]

[0210] This gives the following measurement data:

[0211] [Table 4]

[0212] By adding the compounds HTM5 (I3) or HTM6 (I4) to the HTL containing the compound HTM1, an improvement in lifetime is achieved in each case, as compared to the OLED C3, which contains only the compound HTM1 in the HTL, but otherwise has the same structure.

[0213] A similar improvement in lifetime is observed for OLEDs with a thin HTL (70 nm) compared to the thicker HTL used in OLEDs C3, I3 and I4, as shown by the examples that follow, where, as already mentioned, OLEDs with a mixture of two different materials in the HTL (I6, I7 and I8) are compared to an OLED containing only compound HTM1 in the HTL (C4).

[0214] [Table 5]

[0215] This gives the following measurement data:

[0216] [Table 6]

[0217] In all cases, the addition of a material selected from HTM5, HTM6 and HTM7 improves the lifetime of the OLED.

[0218] The second material can also be added in percentages higher than the 20% shown above, as shown by the following examples:

[0219] [Table 7]

[0220] The following result is obtained:

[0221] [Table 8]

[0222] However, the addition of a high proportion of the second material has the disadvantage that a loss of efficiency occurs. As shown above, when the second material is used in a proportion of 10 to 30% by volume, especially 20% by volume, the loss of efficiency, if any, occurs to a significantly lesser extent.

[0223] [Table 9]

[0224] 4) Determination of HOMO of compounds used in mixed HTL The method described in published specification WO2011 / 032624, p. 28, line 1 to p. 29, line 21, gives the following values ​​for the HOMO of compounds HTM1, HTM2, HTM3, HTM5, HTM6 and HTM7:

[0225] [Table 10]

Claims

1. It is an electronic device, -anode, - Cathode, - A light-emitting layer placed between the anode and cathode, - A hole injection layer positioned between the anode and the light-emitting layer; - Displaced between the hole injection layer and the light-emitting layer, directly adjacent to the light-emitting layer on the anode side, and according to formulas (I) and (II) 【Chemistry 1】 (In the ceremony Z is the same or different in each case, CR １ and are selected from N, where Z is 【Chemistry 2】 If a group is bonded to it, it is C; X is the same or different in each case, single bond, O, S, C(R) １ ) ２ and NR １ Selected from; Ar １ and Ar ２ In each case, they may be the same or different, and each has 6 to 40 aromatic ring atoms, and one or more R ２ Aromatic ring systems substituted by radicals, and having 5 to 40 aromatic ring atoms, with one or more R ２ Selected from heteroaromatic ring systems substituted with radicals; R １ and R ２ are, in each case, the same or different and are selected from H, D, F, Cl, Br, I, C(=O)R ３ , CN, Si(R ３ ), ３ , N(R ３ ), ２ , P(=O)(R ３ ), ２ , OR ３ , S(=O)R ３ , S(=O) ２ R ３ , a straight-chain alkyl or alkoxy group having 1 to {20} carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to {20} carbon atoms, an alkenyl or alkynyl group having 2 to {20} carbon atoms, an aromatic ring system having 6 to {40} aromatic ring atoms, and a heteroaromatic ring system having 5 to {40} aromatic ring atoms; two or more R １ or R ２ radicals may be bonded to each other or may form a ring; the alkyl, alkoxy, alkenyl and alkynyl groups mentioned, and the aromatic ring system and heteroaromatic ring system mentioned are each substituted by an R ３ radical; one or more CH ２ groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by -R ３ C=CR ３ [[ID=三十八]]-, -C≡C-, Si(R ３ ), ２ , C=O, C=NR ３ , -C(=O)O-, -C(=O)NR ３ -, NR ３ , P(=O)(R ３ ), -O-, -S-, SO or SO ２ ; R ３ In each case, these are the same or different and are 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; two or more R ３ The radicals may be bonded to each other or form a ring; the alkyl, alkoxy, alkenyl and alkynyl groups, aromatic ring systems and heteroaromatic ring systems mentioned herein may be substituted with one or more radicals selected from F and CN; n is 0, 1, 2, 3, or 4, and if n = 0, Ar １ (There is no group; the nitrogen atom is directly bonded to the rest of the formula.) A hole transport layer containing two different compounds, HTM-1 and HTM-2, represented by [formula]. Includes, An electronic device characterized in that the hole transport layer has a thickness of 20 nm to 300 nm, HTM-1 has a HOMO of -4.8 eV to -5.2 eV, HTM-2 has a HOMO of -5.1 eV to -5.3 eV, and further characterized in that HTM-1 has a higher HOMO energy level than HTM-2.

2. The electronic device according to claim 1, characterized in that the light-emitting layer is a light-emitting layer that emits blue fluorescence or a light-emitting layer that emits green phosphorescence.

3. The electronic device according to claim 1 or 2, characterized in that the hole transport layer has a layer thickness of 250 nm or less.

4. The electronic device according to any one of claims 1 to 3, characterized in that the hole transport layer contains two strictly different compounds that match the same or different formulas selected from formulas (I) and (II).

5. The electronic device according to any one of claims 1 to 4, characterized in that the hole transport layer is made of a compound that matches the same or different formulas selected from formulas (I) and (II).

6. The electronic device according to any one of claims 1 to 5, characterized in that the hole transport layer contains two different compounds that conform to formula (I).

7. The electronic device according to any one of claims 1 to 6, characterized in that the two different compounds, each matching the same or different formulas selected from formulas (I) and (II), are present in the hole transport layer in a proportion of at least 5% each.

8. One of the two different compounds in the hole transport layer is of formula (I-1-A) and (II-1-A) 【Transformation 3】 The compound HTM-1 is selected from the following, and the other of the two different compounds in the hole transport layer is of the formula (I-1-B), (I-1-C), (I-1-D), (II-1-B), (II-1-C), and (II-1-D) 【Chemistry 4】 The compound selected from is HTM-2. (In the formulas, the groups appearing in formulas (I-1-A) to (I-1-D) and (II-1-B) to (II-1-D) are as defined in claim 1, and the unoccupied positions on spirobifluorene and fluorene are R １ (Substituted by radicals) An electronic device according to any one of claims 1 to 7, characterized in that...

9. The electronic device according to any one of claims 1 to 8, characterized in that HTM-1 is present in the hole transport layer at a ratio 5 to 2 times higher than the ratio of HTM-2 in the hole transport layer.

10. The electronic device according to any one of claims 1 to 9, characterized in that HTM-1 is present in the hole transport layer at a ratio of 65% to 85%, and HTM-2 is present in the hole transport layer at a ratio of 15% to 35%.

11. The electronic device according to any one of claims 1 to 10, characterized in that HTM-1 has a HOMO of -5.0 eV to -5.2 eV.

12. The electronic device according to any one of claims 1 to 11, characterized in that HTM-1 has a HOMO that is 0.02 eV to 0.3 eV higher than HTM-2.

13. The electronic device according to any one of claims 1 to 12, wherein the electronic device has a layer sequence of anode / hole injection layer / hole transport layer / luminescent layer, and the aforementioned layers are directly adjacent to each other.

14. The electronic device according to any one of claims 1 to 13, characterized in that the hole injection layer contains a mixture of a p-dopant and a hole transport material.

15. The hole transport material in the hole injection layer is of formulas (I-1-A) and (II-1-A) 【Transformation 5】 (In the formulas, the groups appearing in formulas (I-1-A) and (II-1-A) are as defined in claim 1, and the unoccupied positions on spirobifluorene and fluorene are R １ (Substituted by radicals) An electronic device according to any one of claims 1 to 14, characterized in that the compound is preferably selected from the compounds defined above, from the compounds of formula (I-1-A).

16. The electronic device according to any one of claims 1 to 15, characterized in that the hole injection layer contains a hexaazatriphenylene derivative or another highly electron-deficient and / or Lewis acid compound, each in a pure form.

17. A method for manufacturing an electronic device according to any one of claims 1 to 16, characterized in that one or more layers of the device are produced from a solution or by sublimation.

18. Use of the electronic device described in any one of claims 1 to 16 as a light source in a display, for lighting applications, or as a light source in medical and / or cosmetic applications.

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