Electronic devices

Abstract

The present application relates to electronic devices that contain an organic layer, which contains a mixture of at least two different compounds.

Description

[Technical Field]

[0001] This application relates to an electronic device comprising an anode, a hole injection layer, a hole transport layer, a light-emitting layer, and a cathode in this order. The hole transport layer contains a first compound selected from spirobifluorenamine and fluorenamine compounds, and a second compound, which differs from the first compound and is also selected from spirobifluorenamine and fluorenamine compounds.

[0002] In the context of this application, the term "electronic device" is understood to mean a so-called organic electronic device that contains an organic semiconductor material as a functional material. More specifically, these are understood to mean OLEDs (organic light-emitting diodes, organic electroluminescent devices). These are electronic devices having one or more layers containing organic compounds that 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] The hole injection layer is understood to be a layer that facilitates the injection of holes from the anode to the hole transport layer of the OLED during the operation of the electronic device. The hole injection layer is preferably directly adjacent to the anode, and on the cathode side, there is one or more hole transport layers directly adjacent to the hole injection layer.

[0004] A hole transport layer is understood to be a layer that can transport holes during the operation of an electronic device. More specifically, in an OLED, it is a layer located between the anode and the light-emitting layer closest to the anode.

[0005] In electronic devices, particularly OLEDs, there is a strong interest in improving performance data, especially lifespan, efficiency, operating voltage, and color purity. However, no completely satisfactory solution has yet been found in these areas.

[0006] Hole transport layers significantly influence the performance data of electronic devices. They may exist as individual hole transport layers between the anode and the light-emitting layer, or as multiple hole transport layers between the anode and the light-emitting layer, for example, two or three hole transport layers.

[0007] Materials for hole transport layers known in the prior art are primarily amine compounds, particularly triarylamine compounds. Examples of such triarylamine compounds include spirobifluorenamine, fluorenamine, indenofluorenamine, phenanthreneamine, carbazoleamine, xanthenamine, spirodihydroacridineamine, biphenylamine, and combinations of these structural elements having one or more amino groups; this is only a selection, and those skilled in the art will recognize further structural classes.

[0008] Currently, it has been found that electronic devices containing an anode, a hole injection layer, a hole transport layer, a light-emitting layer, and a cathode in this order, wherein the hole transport layer contains a first compound selected from spirobifluorenamine and fluorenamine compounds, and a second compound different from the first compound, also selected from spirobifluorenamine and fluorenamine compounds, have 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 aforementioned prior art devices.

[0009] Therefore, this application is, It is an electronic device, -anode, - Cathode, - An emissive layer positioned 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 equations (I) and (II)

[0010] [ka]

[0011] (wherein Z is the same or different in each case and is selected from CR 2 , 1 and N, where Z is

[0012]

Chemical formula

[0013] is C when a group is attached thereto; X is the same or different in each case and is selected from a single bond, O, S, C(R 1 )2 and NR 1 ; Ar 1 and Ar 2 are the same or different in each case and are selected from an aromatic ring system having 6 to 40 aromatic ring atoms and substituted with one or more R 2 radicals, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms and substituted with one or more R 2 radicals; R 1 and R 2 are the same or different in each case 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)2R 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 2Radicals may be bonded to each other or form a ring; the alkyl, alkoxy, alkenyl and alkynyl groups mentioned, as well as the aromatic and heteroaromatic ring systems mentioned, are R 3 It is substituted with a radical; one or more CH2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned are -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 ), may be replaced by -O-, -S-, SO or SO2; 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 Radicals may be bonded to each other or form rings; the alkyl, alkoxy, alkenyl and alkynyl groups, aromatic ring systems 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 if n=0, Ar 1 (There is no group, and the nitrogen atom is directly bonded to the rest of the formula.) A hole transport layer containing two different compounds that match the same or different formulas selected from the available formulas. We provide electronic devices that include [this].

[0014] If n=2, then two Ar 1 The base is -Ar 1 -Ar 1 - is connected in a line consecutively. If n=3, then 3 Ar 1 The base is -Ar 1 -Ar1 -Ar 1 - is connected in a line consecutively. If n=4, then there are 4 Ar 1 The base is -Ar 1 -Ar 1 -Ar 1 -Ar 1 They are joined together in a continuous line as -.

[0015] The definitions that follow are applicable to the chemical groups used in this application. They are applicable unless further specific definitions are given.

[0016] In the context of this invention, the aryl group is understood to mean a single aromatic ring, i.e., benzene, or a fused aromatic polycyclic ring, such as naphthalene, phenanthrene, or anthracene. In the context of this application, a fused aromatic polycyclic ring consists of two or more single aromatic rings fused together. Inter-ring condensation is understood here to mean that the rings share at least one edge with each other. In the context of this invention, the aryl group contains 6 to 40 aromatic ring atoms. In addition, the aryl group does not contain any heteroatoms as aromatic ring atoms.

[0017] In the context of this invention, a heteroaryl group is understood to mean any single heteroaromatic ring, such as pyridine, pyrimidine, or thiophene, or a condensed heteroaromatic polycyclic ring, such as quinoline or carbazole. In the context of this application, a condensed heteroaromatic polycyclic ring consists of two or more single aromatic or heteroaromatic rings fused together, where at least one of the aromatic and heteroaromatic rings is a heteroaromatic ring. Interring condensation is understood here to mean that the rings share at least one edge with each other. In the context of this invention, a heteroaryl group contains 5 to 40 aromatic ring atoms, of which at least one is a heteroatom. The heteroatom of the heteroaryl group is preferably selected from N, O, and S.

[0018] Each of the aryl or heteroaryl groups may be substituted with the radicals mentioned above, in particular benzene, naphthalene, anthracene, phenanthrene, pyrene, dihydropyrene, chrysene, perylene, triphenylene, fluorantene, benzoanthracene, benzophenanthrene, tetracene, pentacene, benzopyrene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, and indo Isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthidine, 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, Nzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, pyrazine, phenazine, naphthyrizine, azacarbazole, benzocarbolin, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole This is understood to mean groups derived from zole, 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, indidine, and benzothiadiazole.

[0019] In the context of the present invention, an aromatic ring system 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 included in this definition are tetrahydronaphthalene, fluorene, and spirobifluorene. In addition, the term “aromatic ring system” includes systems consisting of two or more aromatic ring systems linked to each other via single bonds, such as biphenyl, terphenyl, 7-phenyl-2-fluorenyl, quaterphenyl, and 3,5-diphenyl-1-phenyl. In the context of the present invention, an aromatic ring system contains 6 to 40 carbon atoms in the ring system but does not contain heteroatoms. Heteroaryl groups are not included in the definition of “aromatic ring system”.

[0020] A heteroaromatic ring system conforms to the definition of an aromatic ring system, except that it must contain at least one heteroatom as a ring atom. Similar to aromatic ring systems, a heteroaromatic ring system does not need to contain only aryl and heteroaryl groups, but may additionally contain one or more nonaromatic rings fused to at least one aryl or heteroaryl group. The nonaromatic ring may contain only carbon atoms as ring atoms, or may additionally contain one or more heteroatoms, the heteroatoms preferably selected from N, O, and S. An example of such a heteroaromatic ring system is benzopyranyl. Furthermore, the term “heteroaromatic ring system” is understood to mean a system consisting of two or more aromatic or heteroaromatic ring systems linked to each other via single bonds, such as 4,6-diphenyl-2-triazinyl. In the context of the present invention, a heteroaromatic ring system contains 5 to 40 ring atoms selected from carbon and heteroatoms, at least one of which is a heteroatom. The heteroatoms of a heteroaromatic ring system are preferably selected from N, O, and S.

[0021] Therefore, the terms "heteroaromatic ring system" and "aromatic ring system" as defined in this application differ 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. This heteroatom may exist as a ring atom of a nonaromatic heterocyclic ring or as a ring atom of an aromatic heterocyclic ring.

[0022] According to the above definition, all aryl groups are included in the term "aromatic ring system," and all heteroaryl groups are included in the term "heteroaromatic ring system."

[0023] Aromatic ring systems having 6 to 40 aromatic ring atoms, or heteroaromatic ring systems having 5 to 40 aromatic ring atoms, are understood to mean groups derived from the groups previously mentioned under aryl and heteroaryl groups, and from biphenyl, terphenyl, quaterphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, indenofluorene, torxene, isotorxene, spirotorxene, spiroisotorxene, indenocarbazole, or combinations thereof.

[0024] In the context of the present invention, linear alkyl groups having 1 to 20 carbon atoms, branched or cyclic alkyl groups having 3 to 20 carbon atoms, and alkenyl or alkynyl groups having 2 to 40 carbon atoms may also have individual hydrogen atoms or CH2 groups substituted with groups previously mentioned in the definition of radicals, preferably methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, cyclopentyl, neopentyl This is understood to mean tyl, 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, ethinyl, propynyl, butynyl, pentynyl, hexynyl, or octinyl radical.

[0025] Alkoxy or thioalkyl groups having 1 to 20 carbon atoms may also have individual hydrogen atoms or CH2 groups replaced by groups previously mentioned in the definition of 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, etenylthio, propenylthio, butenylthio, pentenylthio, cyclopentenylthio, hexenylthio, cyclohexenylthio, heptenylthio, cycloheptenylthio, octenylthio, cyclooctenylthio, ethinylthio, propynylthio, butynylthio, pentynylthio, hexynylthio, heptynylthio, or octinylthio.

[0026] The expression that two or more radicals may come together to form a ring is naturally understood in the context of this application to mean, in particular, that two radicals are bonded to each other by chemical bonds. However, it should also be naturally understood that, if one of the two radicals is hydrogen, the second radical will bond 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] A preferred anode for an electronic device is a material with a high work function. Preferably, the anode has a work function greater than 4.5 eV relative to vacuum. Firstly, metals with a high redox potential are suitable for this purpose, such as Ag, Pt, or Au. Secondly, metal / metal oxide electrodes (e.g., Al / Ni / NiO) are suitable. x Al / PtO x ) may also be preferable. Depending on the application, at least one of the electrodes should be transparent or partially transparent to allow either irradiation of an organic material (organic solar cell) 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] A preferred cathode for electronic devices is a multilayer structure composed of a metal, metal alloy, or various metals with a low work function, such as alkaline earth metals, alkali metals, main group metals, or lanthanides (e.g., Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Also preferred are alloys composed of alkali metals or alkaline earth metals with silver, such as magnesium and silver. In the case of multilayer structures, in addition to the metals mentioned, further metals with relatively high work functions, such as Ag or Al, may also be used, in which case combinations of metals such as Ca / Ag, Mg / Ag, or Ba / Ag are commonly used. It may also be preferable to introduce a thin interlayer 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 their 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.

[0030] The light-emitting layer of the device may be either a fluorescent light-emitting layer or a phosphorescent light-emitting layer. Preferably, the light-emitting layer of the device is a fluorescent light-emitting layer, and more preferably a light-emitting layer that emits blue fluorescence. In a fluorescent light-emitting layer, the light-emitting material is preferably a singlet light-emitting material, i.e., a compound that emits light from an excited singlet state when the device is operating. In a phosphorescent light-emitting layer, the light-emitting material is preferably a triplet light-emitting material, 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 operating.

[0031] In a preferred embodiment, the fluorescent emitting layer used is a layer that emits blue fluorescence.

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

[0033] A suitable phosphorescent material is a compound that, when properly excited, preferably emits light in the visible region and also contains at least one atom with an atomic number greater than 20, preferably greater than 38 and less than 84, and more preferably greater than 56 and less than 80. It is preferable to use a compound containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold, or europium as the phosphorescent material, and particularly a compound containing iridium, platinum, or copper.

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

[0035] The following table shows compounds that are preferable for use as phosphorescent materials:

[0036] [ka]

[0037] [ka]

[0038] [ka]

[0039] [ka]

[0040] [ka]

[0041] [ka]

[0042]

change

[0043]

change

[0044]

change

[0045]

change

[0046]

change

[0047] Preferred fluorescent compounds are selected from the class of arylamines. 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 nitrogen. Preferably, at least one of these aromatic or heteroaromatic ring systems is a fused ring system, and more preferably, has at least 14 aromatic ring atoms. These preferred examples are aromatic anthraceneamines, aromatic anthracenediamines, aromatic pyreneamines, aromatic pyrenediamines, aromatic chrysenamines, or aromatic chrysendiamines. Aromatic anthraceneamines are understood to mean compounds in which a diarylamino group is directly bonded to an anthracene group, preferably at position 9. Aromatic anthracenediamines are understood to mean compounds in which two diarylamino groups are directly bonded to an anthracene group, preferably at positions 9 and 10. Aromatic pyreneamines, pyrenediamines, chrysenamines, and chrysendiamines are similarly defined, in which the diarylamino group is bonded to pyrene, preferably at position 1 or position 1 and 6. Further preferred luminescent compounds are indenofluorenamine or diamine, benzoindenofluorenamine or diamine, and dibenzoindenofluorenamine or diamine, as well as indenofluorene derivatives having a condensed aryl group. Equally preferred are pyrenearylamines. Equally preferred are benzoindenofluorenamine, benzofluorenamine, extended benzoindenofluorene, phenoxazine, and fluorene derivatives bonded to a furan unit or a thiophene unit.

[0048] The following table shows compounds that are preferable for use as fluorescent emitters:

[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 an electronic device contains strictly one matrix compound. The 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 called a mixed matrix system and is particularly preferred in the case of a phosphorescent light-emitting layer.

[0060] In the case of a phosphorescent luminescent 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%.

[0061] In this context, percentages are understood to represent volume percentages for layers added from the gas phase and weight percentages for layers added from the solution.

[0062] Accordingly, 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%.

[0063] In the case of a fluorescent luminescent 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%.

[0064] Accordingly, the proportion of the fluorescent luminescent compound is 0.1% to 50.0%, preferably 0.5% to 20.0%, and more preferably 1.0% to 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 having hole transport properties, and the other material is a material having 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 bandgap 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, and most preferably 1:4 to 1:1. It is preferable to use a mixed matrix system for phosphorescent organic electroluminescent devices.

[0066] Preferred matrix materials for fluorescent compounds are selected from the classes of oligoarylenes (e.g., 2,2',7,7'-tetraphenylspirobifluorene), particularly oligoarylenes containing condensed aromatic groups, oligoarylene vinylenes, multi-legged metal complexes, hole-conducting compounds, electron-conducting compounds, particularly ketones, phosphine oxides and sulfoxides; atropisomers, boronic acid derivatives, and benzoanthracenes. Particularly preferred matrix materials are selected from the classes of oligoarylenes containing naphthalene, anthracene, benzoanthracene and / or pyrene or atropisomers of these compounds, oligoarylene vinylenes, ketones, phosphine oxides, and sulfoxides. Very particularly preferred matrix materials are selected from the classes of oligoarylenes containing anthracene, benzoanthracene, benzophenanthrene and / or pyrene or atropisomers of these compounds. In the context of the present invention, oligoarylene is naturally understood to mean a compound in which at least three aryl or arylene groups are bonded to one another.

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

[0068] [ka]

[0069] [ka]

[0070] [ka]

[0071] [ka]

[0072] Preferred matrix materials for phosphorescent media include 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, azabolol or boronic acid esters, triazine derivatives, zinc complexes, diazasilol or tetraazalol derivatives, diazaphosphorol derivatives, crosslinked carbazole derivatives, triphenylene derivatives, or lactams.

[0073] In a preferred embodiment, the electronic device includes exactly one light-emitting layer.

[0074] In an alternative, preferred embodiment, the electronic device includes a plurality of light-emitting layers, preferably two, three, or four light-emitting layers. This is particularly preferred in the case of a white light-emitting electronic device.

[0075] More preferably, the light-emitting layer in this case has several emission maxima as a whole between 380 nm and 750 nm, so that the electronic device emits white light; in other words, various light-emitting compounds that can emit fluorescence or phosphorescence, and that emit blue, green, yellow, orange, or red light, can be used in the light-emitting layer. Particularly preferred is a three-layer system, i.e., a system having three light-emitting layers, where one of the three layers exhibits blue emission in each case, one of the three layers exhibits green emission in each case, and one of the three layers exhibits orange or red emission in each case. For the generation of white light, it may be possible to use individual light-emitting compounds that emit light over a wide wavelength range, rather than multiple light-emitting compounds that emit colored light.

[0076] In a preferred embodiment of the present invention, the electronic device comprises two or three, preferably three, identical or different layer sequences stacked on top of each other, each of which comprises the following layers: a hole injection layer, a hole transport layer, an electron blocking layer, an emitting layer, and an electron transport layer, and at least one, preferably all, of the layer sequences are The following layers, namely, - A hole injection layer positioned between the anode and the light-emitting layer; - A hole transport layer disposed between the hole injection layer and the light-emitting layer, directly adjacent to the light-emitting layer on the anode side, and containing two different compounds that match the same or different formulas selected from formulas (I) and (II). It contains.

[0077] A bilayer composed of adjacent n-CGL and p-CGL is preferably arranged between the layer sequences in each case, with the n-CGL positioned on the anode side and the p-CGL correspondingly on the cathode side. Here, CGL represents 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 class 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. It is even more preferable that the hole transport layer has a thickness of 250 nm or less.

[0079] Preferably, the hole transport layer contains two, three, or four, preferably two or three, and most preferably two, different compounds that match the same or different formulas selected from formulas (I) and (II).

[0080] Preferably, the hole transport layer consists of a compound that conforms to the same or different formulas selected from formulas (I) and (II). "Consists of" here is understood 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 during the OLED manufacturing process.

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

[0082] The p-dopants used in accordance with the present invention are preferably organic electron acceptor compounds that can oxidize one or more other compounds in a mixture.

[0083] Particularly preferred p-dopants are quinodimethane compounds, azaindenofluoradione, azaphenalene, azatriphenylene, I2, metal halides, preferably transition metal halides, metal oxides, preferably metal oxides containing at least one transition metal or a metal of group 3, and transition metal complexes, preferably complexes of Cu, Co, Ni, Pd, and Pt having ligands containing at least one oxygen atom as a binding site. Transition metal oxides are even more preferred as dopants, preferably oxides of rhenium, molybdenum, and tungsten, more preferably Re2O7, MoO3, WO3, and ReO3. (III) Bismuth complexes in an oxidized state, more particularly bismuth(III) complexes having electron-deficient ligands, and even more particularly carboxylate ligands are still preferred.

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

[0085] Preferred p-dopants include, in particular, the following compounds:

[0086] [ka]

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

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

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

[0090] Formulas (I) and / or (II) must follow one or more, preferably all, of the following priority trends: In a preferred embodiment, the compound has a single amino group. An amino group is understood to mean a group having a nitrogen atom with three bonding partners. This is preferably understood to mean a group in which three groups selected from aromatic and heteroaromatic groups are bonded to the nitrogen atom.

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

[0092] Z is preferably CR 1 And here, Z is,

[0093] [ka]

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

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

[0096] The preferred case when n=1 -(Ar 1 ) n -The basis is the following formula:

[0097] [ka]

[0098] [ka]

[0099] [ka]

[0100] [ka]

[0101] [ka]

[0102] [ka]

[0103] (In the formula, the dotted line represents the combination to the remainder of the formula, and the bases at positions indicated as unsubstituted are R, respectively) 2 It is substituted by radicals, and R at these positions 2 (The radical is preferably H.) It matches.

[0104] Ar 2 The group is preferably the same or different in each case and is selected from monovalent groups derived from benzene, biphenyl, terphenyl, quaterphenyl, naphthalene, fluorene, particularly 9,9'-dimethylfluorene and 9,9'-diphenylfluorene, 9-silafluorene, particularly 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, where each monovalent group has one or more R 2 It is substituted by a radical. Or, Ar 2The groups may be the same or different in each case, and may be selected from combinations of groups 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 one or more R groups 2 It is substituted with a radical.

[0105] Particularly preferred Ar 2 The groups are the same or different in each case and are selected from phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, fluorenyl, particularly 9,9'-dimethylfluorenyl and 9,9'-diphenylfluorenyl, benzofluorenyl, spirobifluorenyl, indenofluorenyl, indenocarbazolyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, benzofuranyl, benzothiophenyl, benzo-condensed dibenzofuranyl, benzo-condensed 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, each of which has been mentioned may have one or more R groups. 2 It is substituted with a radical.

[0106] Particularly preferred Ar 2 The bases are the same or different, as shown in the following formula:

[0107] [ka]

[0108]

change

[0109]

change

[0110]

change

[0111]

change

[0112]

change

[0113]

change

[0114]

change

[0115]

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[0116]

change

[0117]

change

[0118]

change

[0119] [ka]

[0120] [ka]

[0121] [ka]

[0122] [ka]

[0123] [ka]

[0124] [ka]

[0125] [ka]

[0126] (In the formula, the base at the position indicated as unsubstituted is R 2 It is substituted by radicals, and R at these positions 2 (Is preferably H, and the bond shown by the dotted line is a bond to the amine nitrogen atom.) Selected from.

[0127] Preferably, R 1 and R 2 In each case, they are the same or different, 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, aromatic ring systems, and heteroaromatic ring systems mentioned are each R 3 It is substituted with radicals; one or more CH2 groups in the alkyl or alkoxy group mentioned are -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 -This may be replaced by:

[0128] Comfortable, R 1 These are the same or different in each case 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 aromatic ring systems and heteroaromatic ring systems mentioned are, respectively, R 3 It is substituted with a radical.

[0129] Comfortable, R 2 In each case, they are the same or different, H, D, F, CN, Si(R 3 )4, selected from linear alkyl groups having 1 to 10 carbon atoms, branched or cyclic alkyl 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, where the alkyl groups, aromatic ring systems and heteroaromatic ring systems mentioned are each R 3 It is substituted with a radical.

[0130] - Z is CR 1 And here, Z is,

[0131] [ka]

[0132] If a group is bonded to it, it is C; - X is a single bond; - Ar 1 In each case, these are the same or different, and in each case, there are one or more R 2 It is a divalent group derived from benzene substituted with a radical; - The subscript n is either 0 or 1; - Ar 2 In each case, the above formula Ar may be the same or different. 2 -1~Ar 2 Selected from -272; - R 1 These are the same or different in each case 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 aromatic ring systems and heteroaromatic ring systems mentioned are, respectively, R 3 It is substituted by radicals; - R 2 In each case, they are the same or different, H, D, F, CN, Si(R 3 )4, selected from linear alkyl groups having 1 to 10 carbon atoms, branched or cyclic alkyl 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, where the alkyl groups, aromatic ring systems and heteroaromatic ring systems mentioned are each R 3 Substituted by radicals This is particularly preferable.

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

[0134] [ka]

[0135] (In the formula, the groups that appear are as defined above, preferably defined according to their preferred embodiments, and the unoccupied positions on spirobifluorene are R 1 substituted by a radical) matches

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

[0137]

Chemical Formula

[0138] (In the formula, the groups that appear are as defined above, preferably defined according to their preferred embodiments, and the unoccupied positions on fluorene are R 1 substituted by a radical) matches

[0139] Preferred embodiments of the 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.

[0140] Preferred embodiments of the 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 two different compounds in the hole transport layer that match the same or different formulas selected from formulas (I) and (II) will be referred to as HTM-1, and the other of two different compounds in the hole transport layer that match the same or different formulas selected from formulas (I) and (II) will be referred to as HTM-2.

[0142] In a preferred embodiment, HTM-1 is a compound of formulas (I-1-A) and (II-1-A)

[0143] [ka]

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

[0145] [ka]

[0146] The formula selected from (wherein the formula, the groups appearing in formulas (I-1-A) to (I-1-D) and (II-1-B) to (II-1-D) are as previously defined, preferably according to their preferred embodiments, and the unoccupied positions on spirobifluorene and fluorene are R 1 (Substituted by radicals). More preferably, HTM-2 conforms to formula (I-1-B) or (I-1-D), most preferably to formula (I-1-D). In an alternative preferred embodiment, HTM-2 conforms to formula (II-1-B) or (II-1-D), most preferably to formula (II-1-D).

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

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

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

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

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

[0152] The HOMO energy level is determined by cyclic voltammetry (CV), i.e., by the method described on pages 28, line 1 to 29, line 21 of Publication WO2011 / 032624.

[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 an electronic device is preferably directly adjacent to the anode. More preferably, 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 / luminescence layer, where the aforementioned layers are directly adjacent to each other.

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

[0164] In a preferred embodiment, the hole injection layer contains a mixture of the above-described p-dopant and a hole transporting material. The p-dopant is preferably present in the hole injection layer at a ratio of 1% to 10%. Here, the hole transporting material is preferably selected from a class of materials known to those skilled in the art as hole transporting materials for OLEDs, particularly triarylamines. Indenofluoreneamine derivatives, amine derivatives, amine derivatives having a condensed aromatic system, monobenzylindenoindenofluoreneamine, dibenzylindenoindenofluoreneamine, spirobifluoreneamine, fluoreneamine, spirodibenzopyranamine, dihydroacridine derivatives, spirodibenzofuran and spirodibenzothiophene, phenanthrene diarylamine, spirotribenzotropone, spirobifluorene having a metaphenyldiamine group, spirobisacridine, xanthene diarylamine, and 9,10-dihydroanthracene spiro compounds having a diarylamino group are particularly preferred.

[0165] Specific compounds preferred for use as the hole transporting material in the hole injection layer are shown in the following table:

[0166]

Chemical formula

[0167]

Chemical formula

[0168]

Chemical formula

[0169] [[ID=SS]]

Chemical formula

[0170]

Chemical formula

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

[0181] Compounds H-1 to H-146 are generally well-suited for use in OLEDs of any design and composition, not just those specified in this application. The compounds exhibit good performance data in OLEDs, particularly good lifetime and good efficiency.

[0182] The hole transport material for the hole injection layer is more preferably selected from spirobifluorenylamines and fluorenylamines, and more preferably from spirobifluorenyl monoamines and fluorenyl monoamines. Here, monoamine is understood to mean a compound containing a single amine group. Most preferably, the hole transport material for the hole injection layer is selected from the compounds of formulas (I-1-A) and (II-1-A) defined earlier, and more preferably from the compounds of formula (I-1-A).

[0183] In an alternative, preferred embodiment, the hole implantation layer preferably contains a hexaazatriphenylene derivative, such as those 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, in particular Bi(III) complexes, in particular Bi(III) carboxylates, such as compound D-13 described above.

[0184] In addition to the cathode, anode, light-emitting layer, hole injection layer, and hole transport layer, the electronic device preferably also contains further layers. These are preferably selected in each case from one or more hole blocking layers, electron transport layers, electron injection 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 are necessarily present. More specifically, the electronic device preferably contains one or more layers selected from electron transport layers and electron injection layers, disposed between the light-emitting layer and the anode. More preferably, the electronic device contains one or more electron transport layers between the light-emitting layer and the cathode, preferably a single electron transport layer and a single electron injection layer in this order, the electron injection layer 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 include, in particular, aluminum complexes, e.g., Alq3; zirconium complexes, e.g., Zrq4; lithium complexes, e.g., 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:

[0187] [ka]

[0188] [ka]

[0189] [ka]

[0190] In a preferred embodiment, the electronic device is characterized by having one or more layers applied by sublimation. In this case, the material is subjected to a vacuum sublimation system. -5 Less than mbar, preferably 10 -6 The initial pressure is applied by deposition at a pressure of less than mbar. However, in this case, the initial pressure can be further reduced, for example, 10 -7 It is also possible to set it to less than mbar.

[0191] Similarly, electronic devices are preferred in which one or more layers are deposited by OVPD (organic vapor deposition) or with the help of carrier gas sublimation. In this case, the material is 10 -5 The material is applied at a pressure of mbar to 1 bar. A special case of this method is OVJP (organic vapor jet printing), in which the material is applied directly by the nozzle and thus structured (e.g., MSArnold et al., Appl. Phys. Lett. 2008, 92, 053301).

[0192] In addition, an electronic device is preferred in which one or more layers are produced from a solution, for example by spin coating, or by any printing method, such as screen printing, flexographic printing, nozzle printing, or offset printing, more preferably by LITI (photo-induced thermal imaging, thermal transfer printing) or inkjet printing. For this purpose, a soluble compound is required. High solubility can be achieved by suitable substitution of the compound.

[0193] The electronic device of the present invention is more preferably manufactured by applying one or more layers from a solution and one or more layers by sublimation.

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

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

[0196] [example] 1) General manufacturing methods for OLEDs and characterization of OLEDs A glass plaque coated with a 50nm thick structured ITO (indium tin oxide) is the substrate to which the OLED is applied.

[0197] OLEDs basically have 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 the cathode. The cathode is formed by a 100 nm thick aluminum layer. The exact structure of an OLED can be found in Table 1.

[0198] All materials are deposited by thermal deposition in a vacuum chamber. Here, the luminescent layer in this example consists of a matrix material (host material) and a luminescent dopant (luminescent material) added to the matrix material in a specific volume ratio by co-deposition. Details given in the form of SMB1:SEB1(5%) mean that material SMB1 is present in the layer at a volume ratio of 95% and material SEB1 at a volume ratio of 5%. Similarly, the electron transport layer, and in certain examples HIL and / or HTL, also consist of a mixture of two materials, and the proportions of the materials are reported as previously specified.

[0199] Table 2 shows the chemical structures of the materials used in OLEDs.

[0200] OLEDs are characterized by standard methods. For this purpose, the electroluminescence spectrum, the external quantum efficiency (EQE, measured in %), which is calculated as a function of luminance from current-voltage-luminance characteristics assuming Lambertian emission characteristics, and the lifetime are determined. Parameter EQE@10mA / cm 2 refers to the external quantum efficiency achieved at 10 mA / cm². Parameter U@10mA / cm² 2 refers to the operating voltage at 10 mA / cm². The lifetime LT is defined as the time until the luminance decreases from the initial luminance to a specific ratio during operation at a constant current density. The number LT80 here means that the recorded lifetime corresponds to the time until the luminance decreases to 80% of its initial value. @60mA / cm² 2 The number @60mA / cm² 2 here means that the relevant lifetime is measured at 60 mA / cm². 2 2

[0201] 2) An OLED containing a mixture of two different materials in the HTL with a p-doped HIL and a comparative example containing a single material in the HTL 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 improvement in efficiency is achieved at the same voltage in OLED I1. Here, it is compared with OLED C1 having the same structure except that the HTL contains only compound HTM3.

[0206] ​​A clear improvement in efficiency is also observed when compound HTM6 is added to an HTL containing HTM2 (OLED I2). Here, we compare it with OLED C2, which contains only compound HTM2 in the HTL but otherwise has the same structure.

[0207] While the improvement in efficiency may be small in terms of percentage figures, it cannot be ignored because achieving such improvements is difficult.

[0208] 3) Comparative example having an HIL composed of a single material, an OLED with a mixture of two different materials in the HTL, and an OLED with a single material in the HTL. Manufacture the following OLEDs:

[0209] [Table 3]

[0210] This gives the following measurement data:

[0211] [Table 4]

[0212] By adding compound HTM5(I3) or HTM6(I4) to an HTL containing compound HTM1, an improvement in lifetime is achieved in each case. Here, we compare it with an OLED C3 containing only compound HTM1, but otherwise having the same structure.

[0213] In the case of OLEDs with a thin HTL (70 nm) compared to the thick HTL used in OLEDC3, I3, and I4, a similar improvement in lifetime is observed, as shown in the following examples. As already mentioned, here we compare OLEDs (I6, I7, and I8) containing a mixture of two different materials in the HTL with an OLED (C4) containing only compound HTM1 in the HTL.

[0214] [Table 5]

[0215] This gives the following measurement data:

[0216] [Table 6]

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

[0218] As shown in the example below, the second ingredient can also be added in a higher proportion than the 20% mentioned earlier:

[0219] [Table 7]

[0220] The following results can be obtained:

[0221] [Table 8]

[0222] However, adding a second material in a high proportion has the disadvantage of causing a decrease in efficiency. As previously shown, when the second material is used in a proportion of 10-30 volume%, and especially 20 volume%, the decrease in efficiency, if any, is clearly at a low level.

[0223] [Table 9]

[0224] 4) Determination of the HOMO of the compound used in the mixed HTL The method described on page 28, line 1 to page 29, line 21 of Publication Specification WO2011 / 032624 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 of the light-emitting layer, and directly adjacent to the hole injection layer on the cathode side of the hole injection layer, and formula (I) or (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 These are the same or different in each case, and are selected from aromatic ring systems having 6 to 40 aromatic ring atoms substituted by one or more R2 groups, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms substituted by one or more R2 groups; R １ is the same or different in each case and is H, D, F, Cl, Br, I, C(=O)R ３ , CN, Si(R ３ ), ３ , 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 R1s 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 R3; one or more CH ２ groups in the alkyl, alkoxy, alkenyl, and alkynyl groups mentioned may be replaced by -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 ; R ２ These are the same or different in each case: H, D, F, Cl, Br, I, C(=O)R ３ , CN, Si(R ３ ) ３ , P(=O)(R ３ ) ２ , OR ３ , S(=O)R ３ , S (=O) ２ R ３ , 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, 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 R2s may be bonded to each other or form a ring; the alkyl, alkoxy, alkenyl and alkynyl groups mentioned, as well as the aromatic ring systems and heteroaromatic ring systems mentioned, are each substituted by R3; and one or more CH3s in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned ２ The base is -R ３ C=CR ３ -, -C≡C-, Si(R ３ ) ２ C=O, C=NR ３ , -C(=O)O-, -C(=O)NR ３ -, P (= O) (R ３ ), -O-, -S-, SO or SO ２ It may be replaced by; R ３ R3 is the same or different in each case and is 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 R3s 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.) It comprises a hole transport layer containing two different compounds, HTM-1 and HTM-2, represented by [formula]; An electronic device characterized in that 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 20 nm to 300 nm.

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

5. The electronic device according to any one of claims 1 to 4, characterized in that the hole transport layer contains two different compounds represented by formula (I) or (II).

6. The electronic device according to any one of claims 1 to 5, characterized in that the hole transport layer is made of a compound represented by formula (I) or (II).

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

8. The electronic device according to any one of claims 1 to 7, characterized in that the two different compounds represented by formula (I) or (II) are each present in the hole transport layer in a proportion of at least 5%.

9. 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 replaced by R1, respectively.) An electronic device according to any one of claims 1 to 8, characterized in that...

10. The electronic device according to any one of claims 1 to 9, characterized in that the HTM-1 has a HOMO of -5.0 eV to -5.2 eV.

11. The electronic device according to any one of claims 1 to 10, characterized in that one of the two different compounds, each matching the same or different formulas selected from formulas (I) and (II), has a HOMO that is 0.02 eV to 0.3 eV higher than the other of the two different compounds, each matching the same or different formulas selected from formulas (I) and (II).

12. The electronic device according to any one of claims 1 to 11, 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.

13. The electronic device according to any one of claims 1 to 12, characterized in that the hole injection layer contains a mixture of a p-dopant and a hole transport material.

14. The hole transport material in the hole injection layer is defined by formulas (I-1-A) and (II-1-A) in claim 9. 【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 replaced by R1, respectively.) The electronic device according to claim 13, characterized in that it is selected from the compounds.

15. The electronic device according to any one of claims 1 to 14, characterized in that the hole injection layer contains a hexaazatriphenylene derivative or another electron-deficient and / or Lewis acid compound, each in a pure form.

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 a solution or by sublimation.

17. Use of the electronic device described in any one of claims 1 to 15 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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