Electronic device

Abstract

To provide an OLED with improved lifetime, efficiency, operating voltage, and color purity.SOLUTION: An electronic device includes an anode, a cathode, an emissive layer disposed between the anode and the cathode, a first hole-transporting layer disposed between the anode and the emissive layer and containing two different compounds that meet the same or different formulas selected from specific formulas (I) and (II), and a second hole-transporting layer disposed between the first hole-transporting layer and the emissive layer.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present application relates to an electronic device comprising, in order, an anode, a first hole-transporting layer, a second hole-transporting layer, a light-emitting layer, and a cathode, wherein the first hole-transporting layer contains a mixture of two different 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 containing organic compounds and emit light when a voltage is applied. The general principles of the structure and function of OLEDs are known to those skilled in the art.

[0003] A hole-transporting layer is understood to be a layer capable of transporting holes during operation of the electronic device. More specifically, a hole-transporting layer is a layer disposed between the anode and an emissive layer in an OLED containing the emissive layer.

[0004] 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, although no completely satisfactory solutions have yet been found in these aspects.

[0005] The hole-transporting layer significantly influences the performance data of the electronic device. It can exist as a separate hole-transporting layer between the anode and the light-emitting layer, or it can exist in the form of multiple hole-transporting layers, for example, two or three hole-transporting layers, between the anode and the light-emitting layer. In addition to its hole-transporting function, the hole-transporting layer can also have an electron-blocking function, meaning that it blocks the movement of electrons from the light-emitting layer to the anode. This function is particularly desirable for the hole-transporting layer directly adjacent to the light-emitting layer on the anode side.

[0006] The materials for hole transport layer known in the prior art are mainly amine compounds, especially triarylamine compounds.The 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, but this is only a list, and those skilled in the art will recognize other structural classes.

[0007] It has now surprisingly been discovered that electronic devices containing an anode, a cathode, a light-emitting layer, a first hole-transporting layer, and a second hole-transporting layer, wherein the first hole-transporting layer contains a mixture of two different compounds, have better performance data than prior art electronic devices in which the first hole-transporting layer is formed from a single compound. More particularly, the lifetime of such devices is improved compared to the prior art devices.

[0008] Therefore, the present application is 1. An electronic device comprising: -anode, cathode, a light-emitting layer disposed between the anode and the cathode; - disposed between the anode and the light-emitting layer, and having formula (I) and (II)

[0009] [ka]

[0010] (In the ceremony Z may be the same or different in each case, and CR 1 and N, where Z is

[0011] [ka]

[0012] If a group is attached to it, it is C; X is the same or different in each occurrence and is a single bond, O, S, C(R 1 )2 and NR 1 Selected from; Ar 1 and Ar 2 are the same or different in each occurrence and have 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 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)2R 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; two or more R 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, and the mentioned aromatic and heteroaromatic ring systems, are each R 3 one or more CH groups in the mentioned alkyl, alkoxy, alkenyl and alkynyl groups may be substituted by -R 3 C=CR 3 -, -C≡C-, Si(R 3 )2, C=O, C=NR 3 , -C(=O)O-, -C(=O)NR 3 -, NR3 , P(=O)(R 3 ), -O-, -S-, SO or SO2; R 3 are the same or different in each occurrence 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; 3 The radicals may be bonded to one another or may form rings; the alkyl, alkoxy, alkenyl and alkynyl groups, aromatic and heteroaromatic ring systems mentioned may be substituted with one or more radicals selected from F and CN; n is 0, 1, 2, 3 or 4, and when n=0, Ar 1 (there is no group present and the nitrogen atom is directly attached to the rest of the formula) a first hole transporting layer containing two different compounds conforming to the same or different formulas selected from: a second hole transport layer disposed between the first hole transport layer and the light emitting layer; An electronic device comprising:

[0013] When n=2, two Ar 1 The group is -Ar 1 -Ar 1 - are bonded in a row. When n=3, three Ar 1 The group is -Ar 1 -Ar 1 -Ar 1 - are bonded 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.

[0014] The following definitions are applicable to chemical groups used in this application unless any further specific definition is given.

[0015] An aryl group in the context of the present invention is understood to mean either a single aromatic ring, i.e., benzene, or a fused aromatic polycycle, such as naphthalene, phenanthrene, or anthracene. A fused aromatic polycycle in the context of the present application consists of two or more single aromatic rings fused to each other. 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. An aryl group does not contain any heteroatoms as aromatic ring atoms.

[0016] 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 heteroatom in the heteroaryl group is preferably selected from N, O, and S.

[0017] The aryl or heteroaryl groups, each of which may be substituted by the above-mentioned radicals, are especially benzene, naphthalene, anthracene, phenanthrene, pyrene, dihydropyrene, chrysene, perylene, triphenylene, fluoranthene, benzanthracene, benzophenanthrene, tetracene, pentacene, benzopyrene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indophenyl, benzophenone, benzoisobenzothiophene, dibenzothiophene, pyrrole, indophenyl, benzophenone, benzoisobenzothiophene, dibenzothiophene, pyrrole, indophenyl, benzophenone, benzoisobenzothiophene, dibenzoisobenzothiophene, pyrrole, indophenyl, benzoisobenzothiophene, benzoisobenzothiophene, dibenzoisobenzothiophene, pyrrole, indophenyl, benzoisobenzothiophene, benzoisobenzothiophene, dibenzoisobenzothiophene, pyrrole, indophenyl, benzoisobenzothiophene, benzoisobenzothiophene, dibenzoisobenzothiophene, pyrrole, indophenyl, benzoisobenzothiophene, benzoisobenzofuran, dibenzoisobenzothiophene, pyrrole, indophenyl ...furan, pyrrole, indophenyl, benzoisobenzofuran, dibenzoiso benzoindole, 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 is understood to mean groups 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.

[0018] An aromatic ring system in the context of this invention does not necessarily contain only aryl groups, but may also contain one or more additional 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. Additionally, the term "aromatic ring system" includes systems consisting of two or more aromatic ring systems bonded to each other via a single bond, such as biphenyl, terphenyl, 7-phenyl-2-fluorenyl, quaterphenyl, and 3,5-diphenyl-1-phenyl. An aromatic ring system in the context of this 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.

[0019] A heteroaromatic ring system conforms to the definition of an aromatic ring system above, except that it must contain at least one heteroatom as a ring atom. As with aromatic ring systems, a heteroaromatic ring system need not contain only aryl and heteroaryl groups, but may also contain one or more additional non-aromatic rings fused to at least one aryl or heteroaryl group. A non-aromatic ring may contain only carbon atoms as ring atoms, or it may contain one or more additional heteroatoms, preferably selected from N, O, and S. An example of such a heteroaromatic ring system is benzopyranyl. Additionally, 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 a single bond, such as 4,6-diphenyl-2-triazinyl. A heteroaromatic ring system in the context of the present invention contains 5 to 40 ring atoms selected from carbon and heteroatoms, with at least one of the ring atoms being a heteroatom. The heteroatoms in a heteroaromatic ring system are preferably selected from N, O, and S.

[0020] 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 either a non-aromatic or aromatic heterocyclic ring.

[0021] 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".

[0022] 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, a radical derived from the radicals mentioned above under the aryl radical and heteroaryl radical, and from biphenyl, terphenyl, quaterphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, indenofluorene, truxene, isotruxene, spirotruxene, spiroisotruxene, indenocarbazole, or a combination of these radicals.

[0023] 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 understood to mean groups in which the individual hydrogen atoms or CH groups may also be substituted by the groups mentioned above in the definition of the radicals, preferably methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, cyclopentyl, neopentyl, ... cyclohexyl, 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 radical.

[0024] In the alkoxy or thioalkyl groups having 1 to 20 carbon atoms, individual hydrogen atoms or CH groups may also be replaced by the groups 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.

[0025] The expression that two or more radicals may join together to form a ring is to be understood in the context of this application to mean, inter alia, that the two radicals are bonded to one another by a chemical bond, but in addition, the expression should also be understood to mean that if one of the two radicals is hydrogen, the second radical is bonded to the position where the hydrogen atom was bonded, thereby forming a ring.

[0026] The electronic device is preferably an organic electroluminescent device (OLED).

[0027] Preferred anodes for electronic devices are materials with a high work function. Preferably, the anode has a work function greater than 4.5 eV vs. vacuum. First, metals with high redox potentials are suitable for this purpose, such as Ag, Pt or Au. Second, 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 light emission (OLEDs, O-lasers). 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.

[0028] Preferred cathodes for electronic devices are metals, metal alloys, or multilayer structures composed of various metals with low work functions, such as alkaline earth metals, alkali metals, main group metals, or lanthanides (e.g., Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Also suitable are alloys composed of alkali metals or alkaline earth metals with silver, such as alloys composed of magnesium and silver. In multilayer structures, in addition to the metals mentioned, additional metals with relatively high work functions, such as Ag or Al, can also be used. In this case, metal combinations such as Ca / Ag, Mg / Ag, or Ba / Ag are commonly used. It may 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 include alkali metal or alkaline earth metal fluorides, as well as the corresponding oxides or carbonates (e.g., LiF, Li2O, BaF2, MgO, NaF, CsF, Cs2CO3, etc.). Lithium quinolinate (LiQ) can also be used for this purpose. The thickness of this layer is preferably 0.5 to 5 nm.

[0029] The light-emitting layer of the device may be a fluorescent light-emitting layer or a 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 a 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 a phosphorescent light-emitting layer, the emitter is preferably a triplet emitter, i.e., a compound that emits light from an excited triplet state or a state with a higher spin quantum number, such as a quintet state, when the device is operated.

[0030] In a preferred embodiment, the fluorescent light-emitting layer used is a blue-fluorescent layer.

[0031] In a preferred embodiment, the phosphorescent light-emitting layer used is a green or red phosphorescent light-emitting layer.

[0032] Suitable phosphorescent emitters are especially compounds which, when appropriately excited, preferably emit light in the visible region 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, preference is given to using compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, especially compounds containing iridium, platinum or copper.

[0033] In general, all such phosphorescent complexes as are 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 devices of the present invention.

[0034] Preferred compounds for use as phosphorescent emitters are shown in the table below:

[0035] [ka]

[0036] [ka]

[0037] [ka]

[0038] [ka]

[0039] [ka]

[0040] [ka]

[0041]

change

[0042]

change

[0043]

change

[0044]

change

[0045]

change

[0046] Preferred fluorescent compounds are selected from the arylamine class. In the context of the present invention, arylamine or aromatic amine is understood to mean a compound 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, and aromatic chrysenediamines. Aromatic anthracenamines are understood to mean compounds in which a diarylamino group is directly bonded to an anthracene group, preferably at the 9-position. Aromatic anthracenediamines are understood to mean compounds in which two diarylamino groups are directly bonded to an anthracene group, preferably at the 9- and 10-positions. Aromatic pyrenamines, pyrenediamines, chrysenamines, and chrysenediamines are similarly defined, with the diarylamino group being bonded to the pyrene, preferably at 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 fused aryl groups. Also preferred are pyrene arylamines. Also preferred are benzoindenofluorene amines, benzofluorene amines, extended benzoindenofluorenes, phenoxazines, and fluorene derivatives linked to furan or thiophene units.

[0047] Preferred compounds for use as fluorescent emitters are shown in the table below:

[0048] [ka]

[0049] [ka]

[0050] [ka]

[0051] [ka]

[0052] [ka]

[0053] [ka]

[0054] [ka]

[0055] [ka]

[0056] 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.

[0057] 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, also referred to as a mixed matrix system, is particularly preferred for phosphorescent light-emitting layers.

[0058] In the case of the phosphorescent light-emitting layer, the total proportion of all matrix materials is preferably 50.0% to 99.9%, more preferably 80.0% to 99.5%, and most preferably 85.0% to 97.0%.

[0059] Figures relating to proportions in % are understood here to mean proportions in % by volume in the case of layers applied from the gas phase and proportions in % by weight in the case of layers applied from solution.

[0060] Correspondingly, the proportion of the phosphorescent compound is preferably 0.1% to 50.0%, more preferably 0.5% to 20.0%, and most preferably 3.0% to 15.0%.

[0061] For the fluorescent-emitting layer, the total proportion of all matrix materials is preferably 50.0% to 99.9%, more preferably 80.0% to 99.5%, and most preferably 90.0% to 99.0%.

[0062] Correspondingly, the proportion of the fluorescent compound is 0.1% to 50.0%, preferably 0.5% to 20.0%, more preferably 1.0% to 10.0%.

[0063] 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 has hole-transporting properties, and the other material has electron-transporting properties. A further matrix material that may be present in the mixed matrix system is a compound with a large energy difference between its HOMO and LUMO (wide bandgap material). 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, and most preferably 1:4 to 1:1. The mixed matrix system is preferably used for phosphorescent organic electroluminescent devices.

[0064] Preferred matrix materials for fluorescent 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 the present invention is understood to mean a compound in which at least three aryl or arylene groups are linked together.

[0065] Preferred matrix materials for fluorescent compounds are shown in the table below:

[0066] [ka]

[0067] [ka]

[0068] [ka]

[0069] [ka]

[0070] 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, diazasilol or tetraazasilol derivatives, diazaphosphole derivatives, bridged carbazole derivatives, triphenylene derivatives, or lactams.

[0071] In preferred embodiments, the electronic device contains exactly one light-emitting layer.

[0072] 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.

[0073] More preferably, the light-emitting layer in this case has several emission maxima between 380 nm and 750 nm as a whole, so that the electronic device emits white light; in other words, various light-emitting compounds that can emit fluorescence or phosphorescence 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 which emits blue light in each case, one of which emits green light in each case, and one of which emits orange or red light in each case. To generate 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.

[0074] 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, and at least one, preferably all, of the layer sequences is The following layers: a light-emitting layer disposed between the anode and the cathode; a first hole-transporting layer disposed between the anode and the light-emitting layer, the first hole-transporting layer containing two different compounds conforming to the same or different formulas selected from formulas (I) and (II), and a second hole-transporting layer disposed between the first hole-transporting layer and the light-emitting layer. Contains:

[0075] A double layer consisting of adjacent n-CGL and p-CGL is preferably arranged between each layer sequence, with the n-CGL disposed on the anode side and the p-CGL disposed on the cathode side. Here, CGL refers to a charge generation layer. Materials used for such layers are known to those skilled in the art. The p-CGL is preferably a p-doped amine, more preferably a material selected from the preferred structural classes of hole transport materials mentioned below.

[0076] The first hole transporting layer preferably has a thickness of 20 nm to 300 nm, more preferably 30 nm to 250 nm, and even more preferably 250 nm or less.

[0077] Preferably, the first hole transporting layer contains exactly two, three or four, preferably exactly two or three, and most preferably exactly two different compounds conforming to the same or different formulas selected from formulas (I) and (II).

[0078] Preferably, the first 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 additional compounds are present in the layer, except for trace amounts of impurities that typically occur as additional compounds in the layer in the manufacturing process of an OLED.

[0079] In an alternative preferred embodiment, in addition to compounds conforming to the same or different formulas selected from formulas (I) and (II), the first hole transporting layer contains a p-dopant.

[0080] 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.

[0081] Particularly preferred p-dopants are quinodimethane compounds, azaindenofluorenediones, azaphenalenes, azatriphenylenes, I2, 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 a binding site. Transition metal oxides are also preferred as dopants, preferably oxides of rhenium, molybdenum, and tungsten, more preferably Re2O7, MoO3, WO3, and ReO3. Even more preferred are complexes of bismuth in the (III) oxidation state, more particularly bismuth(III) complexes with electron-deficient ligands, more particularly carboxylate ligands.

[0082] 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%.

[0083] Preferred p-dopants are especially the following compounds:

[0084] [ka]

[0085] In a preferred embodiment of the invention, the first hole-transporting layer contains two different compounds conforming to formula (I).

[0086] Two different compounds that meet the same or different formulas selected from formulas (I) and (II) are preferably present in the first hole-transporting layer in a proportion of at least 5% each. They are more preferably present in a proportion of at least 10%. One of the compounds is preferably 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 particularly true when the first hole-transporting layer contains exactly two compounds that meet the same or different formulas selected from formulas (I) and (II). Preferably, the proportion of one of the compounds in the layer is 15% to 35%, and the proportion of the other of the two compounds in the layer is 65% to 85%.

[0087] Of formulas (I) and (II), formula (I) is preferred.

[0088] Formula (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 having a nitrogen atom with three binding partners. This is preferably understood to mean a group in which three groups selected from aromatic and heteroaromatic groups are bound to the nitrogen atom.

[0089] In an alternative preferred embodiment, the compound has exactly two amino groups.

[0090] Z is preferably CR 1 where Z is

[0091] [ka]

[0092] If a group is attached to it, it is C; X is preferably a single bond; Ar 1 are preferably the same or different in each occurrence and are 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 It is most preferably substituted by the radical Ar 1 are the same or different in each case, and in each case, one or more R 2 It is a divalent group derived from benzene substituted by a radical. 1 The groups may be the same or different in each case.

[0093] The index n is preferably 0, 1 or 2, more preferably 0 or 1, and most preferably 0.

[0094] When n=1, the preferred -(Ar 1 ) n The - group has the formula:

[0095] [ka]

[0096] [ka]

[0097] [ka]

[0098] [ka]

[0099] [ka]

[0100] [ka]

[0101] (wherein the dotted line represents the bond to the remainder of the formula, and the groups at positions shown as unsubstituted are each R 2 are substituted by radicals, and R 2 The radical is preferably H. matches.

[0102] 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 combinations 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.

[0103] 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.

[0104] Particularly preferred is Ar 2 The groups may be the same or different and have the formula:

[0105] [ka]

[0106]

change

[0107]

change

[0108]

change

[0109]

change

[0110]

change

[0111]

change

[0112]

change

[0113]

change

[0114]

change

[0115]

change

[0116]

change

[0117] [ka]

[0118] [ka]

[0119] [ka]

[0120] [ka]

[0121] [ka]

[0122] [ka]

[0123] (wherein the group at the position shown as unsubstituted is R 2 are substituted by radicals, and R 2 is preferably H, and the dotted bond is the bond to the amine nitrogen atom) is selected from.

[0124] 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, selected from linear alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 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; the alkyl and alkoxy groups, the aromatic ring systems, and the heteroaromatic ring systems are each selected from R 3 one or more CH groups in the mentioned alkyl or alkoxy groups may be substituted by -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

[0125] More preferably, R 1 are in each occurrence the same or different and are selected from H, D, F, CN, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; the mentioned aromatic ring systems and the mentioned heteroaromatic ring systems are each R 3 It is substituted by a radical.

[0126] 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, wherein the alkyl group, the aromatic ring system, and the heteroaromatic ring system are each selected from R 3 It is substituted by a radical.

[0127] - Z is CR 1 where Z is

[0128] [ka]

[0129] If a group is attached to it, it is C; - X is a single bond; - Ar 1 are the same or different in each case, and in each case, one or more R 2 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 defined 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, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; the mentioned aromatic ring systems and the mentioned heteroaromatic ring systems are each 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, wherein the alkyl group, the aromatic ring system, and the heteroaromatic ring system are each selected from R 3 Substituted by a radical It is particularly preferred that

[0130] Formula (I) is preferably formula (I-1)

[0131] [ka]

[0132] wherein 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).

[0133] Formula (II) is preferably formula (II-1)

[0134] [ka]

[0135] wherein the occurring groups are as defined above, preferably according to their preferred embodiments, and unoccupied positions on the fluorene are occupied by R 1 (substituted by radicals) matches.

[0136] Preferred embodiments of compounds of formula (I) are the 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.

[0137] Preferred embodiments of compounds of formula (II) are the compounds cited as exemplary structures in WO2014 / 015937, WO2014 / 015938, WO2014 / 015935 and WO2015 / 082056.

[0138] Hereinafter, one of the two different compounds in the first hole transporting 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 first hole transporting layer that meet the same or different formula selected from formulas (I) and (II) will be referred to as HTM-2.

[0139] In a preferred embodiment, HTM-1 is represented by the formula (I-1-A) and (II-1-A)

[0140] [ka]

[0141] 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)

[0142] [ka]

[0143] wherein the groups appearing in formulae (I-1-A) to (I-1-D) and (II-1-A) 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 (substituted by a radical). More preferably, HTM-2 conforms to formula (I-1-B) or (I-1-D), most preferably formula (I-1-D). In an alternative preferred embodiment, HTM-2 conforms to formula (II-1-B) or (II-1-D), most preferably formula (II-1-D).

[0144] Preferably, HTM-1 is present in the first hole transporting layer in a proportion that is 5 to 2 times higher than the proportion of HTM-2 in the layer.

[0145] Preferably, HTM-1 is present in the layer in a proportion of 50% to 95%, more preferably in a proportion of 60% to 90%, and most preferably in a proportion of 65% to 85%.

[0146] Preferably, HTM-2 is present in the layer in a proportion of 5% to 50%, more preferably in a proportion of 10% to 40%, and most preferably in a proportion of 15% to 35%.

[0147] 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%.

[0148] In a preferred embodiment, HTM-1 has a HOMO of -4.8 eV to -5.2 eV, and HTM-2 has a HOMO of -5.1 eV to -5.4 eV. More preferably, HTM-1 has a HOMO of -5.0 to -5.2 eV, and HTM-2 has a HOMO of -5.1 to -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 that is 0.02 to 0.3 eV higher than HTM-2. "Higher HOMO" is understood here to mean a less negative value in eV.

[0149] 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.

[0150] Preferred embodiments of compound HTM-1 are shown in the table below:

[0151] [ka]

[0152] [ka]

[0153] [ka]

[0154] Preferred embodiments of compound HTM-2 are shown in the table below:

[0155] [ka]

[0156] [ka]

[0157] [ka]

[0158] [ka]

[0159] The second hole transporting layer is preferably directly adjacent to the light-emitting layer on the anode side, and more preferably directly adjacent to the first hole transporting layer on the cathode side.

[0160] The second hole transporting layer preferably has a thickness of 2 to 100 nm, more preferably 5 to 40 nm.

[0161] The second hole-transporting layer preferably contains a compound of formula (I-1-B), (I-1-D), (II-1-B) or (II-1-D) as defined above, more preferably of formula (I-1-D) or (II-1-D). In an alternative preferred embodiment, the second hole-transporting layer contains a compound of formula (III)

[0162] [ka]

[0163] (In the formula: Y is the same or different in each occurrence and is O, S, or NR 1 Selected from; Ar 3 are the same or different in each occurrence and are selected from phenyl, biphenyl, and terphenyl, each of which is R 1 is substituted by a radical; k is 1, 2 or 3; i, in each occurrence, is the same or different and is selected from 0, 1, 2, and 3; The formula is R at each unoccupied position. 1 (substituted by radicals) It contains the compound:

[0164] Preferably, in formula (III), Y, in each occurrence, is the same or different and is selected from O and S, more preferably from O. Even more preferably, k is 1 or 2. Even more preferably, i, in each occurrence, is the same or different and is selected from 1 and 2, more preferably 1.

[0165] The second hole transporting layer preferably consists of a single compound.

[0166] In addition to the cathode, anode, light-emitting layer, first hole-transporting layer, and second hole-transporting layer, the electronic device preferably also contains further layers. These are preferably selected in each case from one or more hole-injection layers, hole-transport layers, hole-blocking layers, electron-transport layers, electron-injection layers, electron-blocking layers, exciton-blocking layers, intermediate layers, charge-generation layers, and / or organic or inorganic p / n junctions. However, it should be noted that not all of these layers necessarily need to be present. More specifically, the electronic device preferably contains one or more layers selected from an electron-transporting layer and an electron-injecting layer disposed 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 electron-injecting layer is preferably directly adjacent to the cathode.

[0167] In particular, the electronic device preferably contains a hole injection layer between the anode and the first hole transport layer and directly adjacent to the anode. The hole injection layer preferably contains a hexaazatriphenylene derivative as described in US2007 / 0092755, or a highly electron-deficient and / or Lewis acidic compound, in pure form, i.e., not as a mixture with another compound. Examples of such compounds include bismuth complexes, particularly Bi(III) complexes, especially Bi(III) carboxylates, such as compound D-13 above.

[0168] In an alternative 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 preferably present in the hole injection layer in a proportion of 1% to 10%. The hole transport material is preferably selected from the class of materials known to those skilled in the art as hole transport materials for OLEDs, in particular triarylamines.

[0169] The arrangement of layers in the electronic device is preferably as follows: -anode- -Hole injection layer- -First hole transport layer- -Optionally further hole transport layer(s)- -Second hole transport layer- -Emitting layer- -Optional hole blocking layer- -Electron transport layer- -Electron injection layer- -Cathode-.

[0170] Materials for the hole injection layer and for any further hole transport layers are preferably selected from indenofluoreneamine derivatives, amine derivatives, hexaazatriphenylene derivatives, amine derivatives with fused aromatic systems, monobenzoindenofluoreneamines, dibenzoindenofluoreneamines, spirobifluoreneamines, fluoreneamines, spirodibenzopyranamines, dihydroacridine derivatives, spirodibenzofurans and spirodibenzothiophenes, phenanthrediarylamines, spirotribenzotropolones, spirobifluorenes with metaphenyldiamine groups, spirobisacridines, xanthenediarylamines and 9,10-dihydroanthracene pyrocompounds with diarylamino groups.

[0171] Specific compounds preferred for use in the hole injection layer and any other hole transporting layers that are optionally present are shown in the table below:

[0172] [ka]

[0173] [ka]

[0174] [ka]

[0175] [ka]

[0176] [ka]

[0177] Suitable materials for the hole-blocking layer, electron-transporting layer, and electron-injecting layer of electronic devices are, inter alia, aluminum complexes such as Alq3, zirconium complexes such as Zrq4, 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 shown in the table below:

[0178] [ka]

[0179] [ka]

[0180] [ka]

[0181] In a preferred embodiment, the electronic device is characterized in that one or more layers are applied by sublimation, in which case the material is applied in a vacuum sublimation system at 10 -5 less than mbar, preferably 10 -6 It is applied by evaporation at an initial pressure of less than 10 mbar, but in this case the initial pressure can be lowered further, for example to 10 -7 It is also possible to have a pressure below mbar.

[0182] Likewise, electronic devices are preferred, 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-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 is therefore structured (for example, MS Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

[0183] In addition, preferred are electronic devices 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.

[0184] More preferably, the electronic device of the present invention is fabricated by applying one or more layers from solution and applying one or more layers by sublimation.

[0185] 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.

[0186] 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.

[0187] [example] 1) General manufacturing method of OLED and evaluation of OLED characteristics A glass plaque coated with 50 nm thick structured ITO (indium tin oxide) is the substrate onto which the OLED is applied.

[0188] An OLED basically has the following layer structure: substrate / hole injection layer (HIL) / hole transport layer (HTL) / electron blocking layer (EBL) / emissive layer (EML) / electron transport layer (ETL) / electron injection layer (EIL), and finally a cathode. The cathode is formed by a 100 nm thick aluminum layer. The exact structure of the OLED can be found in Table 1.

[0189] All materials are applied by thermal evaporation in a vacuum chamber. Here, the light-emitting layer, in this example, consists of a matrix material (host material) and a light-emitting dopant (emitter) that is added to the matrix material by co-evaporation in a specific volumetric proportion. Details given in the form SMB1:SEB1(3%) here mean that the material SMB1 is present in the layer in a volumetric proportion of 97% and the material SEB1 in a volumetric proportion of 3%. Similarly, the electron-transporting layer, and in this example, the HTL, also consists of a mixture of two materials, with the material proportions reported as specified above.

[0190] The chemical structures of the materials used in OLEDs are shown in Table 2.

[0191] The OLEDs are characterized by standard methods. For this purpose, the electroluminescence spectrum, the operating voltage and the lifetime are determined. The parameter U@10 mA / 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 number LT80 here means that the recorded lifetime corresponds to the time until the luminance drops to 80% of its initial value. @60mA / cm 2 The figure here indicates that the relevant life is 60mA / cm 2 This means that the temperature is measured at

[0192] 2) OLEDs with a mixture of two different materials in the HTL and a comparative example with a single material in the HTL OLEDs containing a mixture of two different materials in the HTL and comparative OLEDs containing a single material in the HTL are fabricated in each case; see the table below:

[0193] [Table 1]

[0194] In comparison of OLEDs I1 and I2 with OLED C1 containing pure material HTM1 in the HTL, the addition of material HTM2 (I1) or HTM4 (I2) leads to a clear improvement in lifetime with virtually no change in operating voltage.

[0195] Comparing OLEDs I3, I4 and I5 with OLED C2 containing pure material HTM1 in the HTL, the addition of materials HTM2 (I3) or HTM4 (I4) or HTM8 (I5) leads to a clear improvement in lifetime with virtually no change in operating voltage.

[0196] The same is true for the comparison of I6, I7 and I8 with C3, and I9, I10 and I11 with C4.

[0197] The four test series differ in the material in the EBL (HTM2, HTM4, HTM8, or HTM9), which indicates that the effect of improving lifetime occurs over a wide range of applications where the material in the EBL is different.

[0198] [ka]

[0199] [Table 2]

[0200] 3) Determination of the HOMO of compounds used in mixed HTL The method described in published specification WO2011 / 032624, page 28, line 1 to page 29, line 21, gives the following values ​​for the HOMOs of compounds HTM1, HTM2, HTM4 and HTM8:

[0201] [ka]

Claims

1. 1. An electronic device comprising: -anode, cathode, a light-emitting layer disposed between the anode and the cathode; disposed between the anode and the light-emitting layer and having formulas (I) and (II) 【Chemistry 1】 (In the ceremony Z is the same or different in each occurrence, and CR １ and N, where Z is 【Chemistry 2】 When 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 and have 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 and one or more R ２ heteroaromatic ring systems substituted by radicals; R １ and R ２ are in each case the same or different 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 bonded to each other or may form a ring; the alkyl, alkoxy, alkenyl and alkynyl groups mentioned, and the aromatic and heteroaromatic ring systems mentioned, are each R ３ and substituted by one or more CH radicals in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned above. 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 in each occurrence 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; ３ the radicals may be bonded to one another or may form rings; 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 rest of the formula. a first hole transporting layer containing two different compounds conforming to the same or different formulas selected from: a second hole transport layer disposed between the first hole transport layer and the light emitting layer; Electronic devices including:

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

3. 3. The electronic device according to claim 1, wherein the first hole transporting layer has a thickness of 20 nm to 300 nm.

4. 4. The electronic device according to claim 1, wherein the first hole transporting layer has a thickness of 250 nm or less.

5. 5. The electronic device according to claim 1, wherein the first hole transporting layer contains exactly two different compounds conforming to the same or different formulas selected from formulas (I) and (II).

6. 6. The electronic device according to claim 1, wherein the first hole transporting layer is made of a compound having the same or different formula selected from formulas (I) and (II).

7. 7. The electronic device of claim 1, wherein the first hole transporting layer comprises two different compounds conforming to formula (I).

8. 8. The electronic device according to claim 1, wherein the two different compounds having the same or different formulas selected from formulas (I) and (II) are present in the first hole transporting layer in a proportion of at least 5% each.

9. One of the two different compounds in the first hole transporting layer is represented by the formula (I-1-A) and (II-1-A): 【Transformation 3】 and the other of the two different compounds in the first hole transporting layer is a compound HTM-1 that meets a formula selected from the formulas (I-1-B), (I-1-C), (I-1-D), (II-1-B), (II-1-C), and (II-1-D). 【Chemistry 4】 Compound HTM-2 conforming to the formula selected from (wherein the groups appearing in formulae (I-1-A) to (I-1-D) and (II-1-A) to (II-1-D) are as defined in claim 1, and unoccupied positions on the spirobifluorene and fluorene are each R １ substituted by radicals) 9. The electronic device according to claim 1, wherein the first electrode is a conductive material.

10. 10. The electronic device of claim 9, wherein HTM-1 is present in said first hole-transporting layer in a proportion that is 5 to 2 times higher than the proportion of HTM-2 in said layer.

11. 11. The electronic device according to claim 9, wherein HTM-1 is present in said layer in a proportion of 65% to 85% and HTM-2 is present in said layer in a proportion of 15% to 35%.

12. 12. The electronic device according to claim 9, wherein HTM-1 has a HOMO of −4.8 eV to −5.2 eV, and HTM-2 has a HOMO of −5.1 eV to −5.4 eV.

13. 13. The electronic device according to claim 9, wherein HTM-1 has a HOMO that is 0.02 eV to 0.3 eV higher than that of HTM-2.

14. 14. The electronic device according to claim 1, wherein the second hole transporting layer is directly adjacent to the light-emitting layer on the anode side and directly adjacent to the first hole transporting layer on the cathode side.

15. The second hole transporting layer is represented by formula (I-1-B), (I-1-D), (II-1-B) or (II-1-D): 【Transformation 5】 (wherein the groups appearing in formulae (I-1-B), (I-1-D), (II-1-B) and (II-1-D) are as defined in claim 1, and unoccupied positions on the spirobifluorene and fluorene are R １ substituted by radicals) or the second hole transporting layer contains a compound represented by formula (III): 【Transformation 6】 (In the formula: Y in each occurrence is the same or different and is selected from the group consisting of O, S and NR １ Selected from: Ar ３ are the same or different in each occurrence and are selected from phenyl, biphenyl, and terphenyl, each of which is R １ is substituted by a radical; k is 1, 2 or 3; i, in each occurrence, is the same or different and is selected from 0, 1, 2, and 3; The formula is R at each unoccupied position. １ substituted by radicals) 15. The electronic device according to claim 1, comprising a compound represented by the formula:

16. A method for manufacturing an electronic device according to any one of claims 1 to 15, characterized in that one or more layers of the device are produced from solution or by sublimation.

17. Use of an electronic device according to any one of claims 1 to 15 in a display, as a light source in lighting applications, or as a light source in medical and / or cosmetic applications.

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