Electronic device, display device, method for manufacturing the same and a connection

Abstract

Electronic device comprising: a hole injection layer and / or a hole transport layer and / or a hole-generating layer, wherein at least one of the hole injection layer, the hole transport layer and the hole-generating layer comprises a coordination complex comprising at least one electropositive atom M and at least one anionic methide ligand L represented by the following formula (I): wherein A 1 , A 2 and A 3 each were selected independently from the group consisting of (i) partially or fully halogenated C4 to C 30 -tertiary aliphatic or alicyclic hydrocarbyl, (ii) C6 to C 30 -Aryl, (iii) C2 to C 30 -Heteroaryl, (iv) C1 to C 30 - Sulfonyl, and M is selected from the group consisting of a) Li, Na, K, Rb, Cs, each in oxidation state (I), and b) Be, Mg, Ca, Sr, Ba, Mn, Fe, Co, Ni, Zn, Cd, Sn, Pb, each in oxidation state (II), where A 1 , A 2 and A 3 are substituted with fluorine, and wherein in A 1 , A 2 and A 3 the ratio of fluorine : hydrogen ≥ 1.

Description

[0001] The present invention relates to an electronic device, a display device comprising the electronic device, a method for manufacturing the electronic device or the display device, a semiconducting material and a compound. TECHNICAL BACKGROUND

[0002] Organic light-emitting diodes (OLEDs), which are self-emitting devices, feature wide viewing angles, excellent contrast, fast response, high brightness, excellent operating voltage characteristics, and color rendering. A typical OLED includes an anode, a hole-transport layer (HTL), an emission layer (EML), an electron-transport layer (ETL), and a cathode, which are sequentially stacked on a substrate. In this context, the HTL, EML, and ETL are thin layers formed from organic and / or organometallic compounds.

[0003] When a voltage is applied to the anode and cathode, the holes injected from the anode electrode move through the HTL into the EML, and the electrons injected from the cathode electrode move through the ETL into the EML. The holes and electrons recombine in the EML to produce excitons. When the excitons decay from an excited state to a ground state, light is emitted. The injection and flow of holes and electrons should be balanced so that an OLED with the structure described above has excellent efficiency.

[0004] WO 2017 / 029370 A1 and WO 2007 / 029366 A1 disclose the use of sulfonylimide metal complexes as hole-injecting materials.

[0005] US 2013 / 037753 A1 discloses polymeric hole-transporting semiconducting materials comprising ammonium, phosphonium, carbonium, sulfonium or iodonium methide salts.

[0006] EP 2 966 942 A1 discloses a treatment liquid containing an ionic compound and a solvent and used for adhering the ionic compound to at least one surface selected from the group consisting of a surface on which a layer having hole transport properties is to be formed and a surface of a layer having hole transport properties.

[0007] US 5 273 840 A discloses methide salts and their use in batteries.

[0008] However, there remains a need to improve the performance of electronic devices and / or optoelectronic devices, in particular optoelectronic devices comprising an organic charge transport material, such as organic light-emitting diodes (OLEDs) or organic photovoltaic (OPV) devices, and in complex devices such as OLED displays comprising these optoelectronic devices.

[0009] The object of the present invention is therefore to provide an electronic device and a method for manufacturing the same which overcomes the disadvantages of the prior art, in particular to provide electronic devices which comprise hole transport materials, hole injecting materials, hole generating materials or two or more thereof, for improving the performance of the device, in particular for improving voltage, efficiency or lifetime thereof. SUMMARY OF THE INVENTION

[0010] The above object is achieved by an electronic device comprising: a hole injection layer and / or a hole transport layer and / or a hole generating layer, wherein at least one of the hole injection layer, the hole transport layer and the hole generating layer comprises a coordination complex comprising at least one electropositive atom M and at least one anionic methide ligand L represented by the following formula (I): wherein A 1 , A 2 and A 3 each independently selected from the group consisting of (i) partially or fully halogenated C4 to C 30 -tertiary aliphatic or alicyclic hydrocarbyl, (ii) C6 to C 30 -, alternatively C4- to C 12 -Aryl, (iii) C2 to C 30 -, alternatively C4- to C 12 -Heteroaryl, (iv) C1 to C 30 -, alternatively C1- to C 12 -sulfonyl, and

[0011] M is selected from the group consisting of a) Li, Na, K, Rb, Cs, each in the oxidation state (I), b) Be, Mg, Ca, Sr, Ba, Mn, Fe, Co, Ni, Zn, Cd, Sn, Pb, each in the oxidation state (II), where A 1 , A 2 and A 3 are substituted with fluorine, and where in A 1 , A 2 and A 3 the number ratio of fluorine : hydrogen is ≥ 1.

[0012] It has been surprisingly discovered by the inventors that coordination complexes as defined above, when used in the hole-injection layer, the hole-transport layer, or the hole-generating layer of an electronic device, can be useful for improving the performance thereof, in particular with regard to the operating voltage, quantum efficiency, and lifetime thereof. Likewise, it has been surprisingly discovered by the inventors that the coordination complexes defined herein can be successfully used as alternative materials for the fabrication of electronic devices, in particular semiconducting devices described herein, and therefore offer a multitude of possibilities by bringing further degrees of freedom to the development of organic semiconducting materials, (organic) electronic devices, and the like.

[0013] It should be understood that the term "semiconducting" in this context refers to materials and / or devices with an electronic conduction mechanism. The electric current in semiconductors can be interpreted as a flow of mobile electrons. This is distinct from electrical devices that utilize ionic conductivity. Such devices (not according to the invention), e.g., galvanic cells, comprise an electrolyte with mobile ions, and the electric current therein is accompanied by an ionic current through the electrolyte.

[0014] It is to be understood that the term “electrical properties” refers to injection and / or transport of electrons in semiconducting materials and layers included in the device defined herein.

[0015] The electronic device according to the invention is an organic electronic device comprising at least one organic semiconductor layer, usually a plurality of organic semiconductor layers. These layers can be produced, for example, by evaporating a chemical compound and depositing it on a support (or a preceding layer) to form the layer. According to the invention, at least one of the layers of the device is a hole-injection layer, a hole-transport layer, or a hole-generating layer and comprises the coordination complex as defined herein. In this context, it can be provided that the coordination complex is comprised in the layer in addition to another material, for example in the case that the coordination complex is a dopant which is comprised in the layer together with a suitable matrix compound.It can also be provided that the corresponding layer consists of the coordination complex, i.e., that the layer does not comprise any further components (except for impurities that cannot be prevented by conventional technical means). In such a case that the layer consists of the coordination complex, the respective layer can be the hole-injection layer.

[0016] If the coordination complex is an electrical dopant, the electrical dopant (which may be embedded in a charge-transport matrix compound) can enhance the electrical conductivity of the matrix material and / or the injection of an electrical charge into it. The matrix material is the predominant material in such a layer.

[0017] It should be understood that the term "electrical dopant" as used herein refers to a compound that improves the electrical properties of a semiconducting material and / or layer. As a result, the conductivity, operating voltage, voltage rise over time, efficiency, and / or lifetime of a device comprising the doped semiconducting material and / or layer may be improved. The electrical dopant may be non-emissive.

[0018] In the electronic device, the at least one layer comprising the coordination complex may be solid.

[0019] In the electronic device, the at least one layer comprising the coordination complex may be amorphous. In this context, a bulk material having a glass transition temperature above room temperature, measured by a standard method, is assumed to form an amorphous layer if the layer is prepared by the same method as the bulk material (e.g., vacuum deposition or by evaporating a solution of the material in a specific solvent). The standard method is described in the experimental section.

[0020] The layer comprising the coordination complex can be non-emissive.

[0021] In the electronic device according to the invention, the coordination complex may have the general formula (II). M n L m Q p O1 (II) where M and L are as defined above; Q is a ligand different from L; n is from 1 to 4; m from 1 to 6; p is from 0 to 6; and 10 or 1.

[0022] In this way, it is possible to further improve the properties of the electronic device, in particular with regard to operating voltage, efficiency and / or lifetime thereof.

[0023] In the electronic device according to the invention, M can be selected from a) Li, Na, K, Rb, Cs, each in the oxidation state (I), and b) Mg, Ca, Sr, Ba, Mn, Fe, Co, Ni, Zn, each in oxidation state (II). Alternatively, Li in oxidation state (I) and Mg, Ca, Sr, Mn, Zn, each in oxidation state (II). In this way, it is possible to further improve the properties of the electronic device, particularly with regard to operating voltage, efficiency, and / or lifetime.

[0024] In the electronic device, A 1 , A 2 and A 3substituted with fluorine substituents. The numerical ratio of fluorine: hydrogen in A 1 , A 2 and A 3 ist ≥ 1. In this way, it is possible to further improve the properties of the electronic device, in particular with regard to operating voltage, efficiency and / or lifetime thereof.

[0025] In the electronic device according to the invention, m can be 2 to 4. In this way, it is possible to further improve the properties of the electronic device, in particular with regard to operating voltage, efficiency and / or lifetime thereof.

[0026] In the electronic device according to the invention, at least one of A 1 , A 2 and A 3 from C1 to C 30 -sulfonyl, alternatively from C1 to C 12 -sulfonyl and CN. Alternatively, one or two of A 1 , A 2 and A 3 C1 to C 30-Sulfonyl. Alternatively, one or two of A 1 , A 2 and A 3 C1 to C 12 -Sulfonyl. The sulfonyl can be partially or fully halogenated, alternatively partially or fully fluorinated, or alternatively perfluorinated. This makes it possible to further improve the properties of the electronic device, particularly with regard to operating voltage, efficiency, and / or lifetime.

[0027] In the electronic device according to the invention, at least one of A 1 , A 2 and A 3 from C6 to C 30 -aryl and C2-to C 30-Heteroaryl, wherein the aryl or heteroaryl may be substituted with substituents selected from the group consisting of CN, F, Cl, Br, and I; and in this case, the ratio of substituents:hydrogen in the aryl or heteroaryl may be ≥ 1. In this way, it is possible to further improve the properties of the electronic device, in particular with regard to operating voltage, efficiency, and / or lifetime thereof.

[0028] In the electronic device according to the invention, the hole-injection layer and / or the hole-generating layer may comprise more than 50% by weight and / or volume of the coordination complex; alternatively, the hole-injection layer and / or the hole-generating layer may comprise more than 80% by weight and / or volume of the coordination complex; alternatively, more than 90%, alternatively, more than 95%, alternatively, more than 98%, alternatively, more than 99%. In this way, it is possible to further improve the properties of the electronic device, in particular with regard to operating voltage, efficiency, and / or lifetime thereof.

[0029] In the electronic device according to the invention, A 1 , A 2 and A 3each independently selected from the group consisting of CF3SO2, C6F5, C6H5, C4F9SO2, C6F4CF3, and C3NF4. In this way, it is possible to further improve the properties of the electronic device, in particular with regard to operating voltage, efficiency, and / or service life thereof.

[0030] In the electronic device according to the invention, the coordination complex may be one or more of the following formulas

[0031] With regard to the exemplary formulas, it is to be understood that, particularly with regard to the binding of the ligands to metal atoms, the depicted formulas cannot accurately reflect the real binding mode and should therefore be taken as representations of metal-ligand ratios that may apply to complexes enabling exemplary embodiments of the invention.

[0032] By using the exemplary complexes, it is possible to further improve the properties of the electronic device, in particular with respect to operating voltage, efficiency and / or lifetime thereof.

[0033] The electronic device according to the invention may be an organic electronic device, in particular an organic electroluminescent device, an organic transistor or an organic photovoltaic device.

[0034] In the electronic device, at least one light-emitting layer or at least one light-absorbing layer can be arranged between the first electrode and the second electrode, wherein the first electrode is an anode and the layer comprising the coordination complex is arranged between the anode and the light-emitting layer, or between the anode and the light-absorbing layer.

[0035] In the electronic device, the layer comprising the coordination complex may be adjacent to the anode.

[0036] The above analysis is further solved by a display device comprising at least two devices according to the invention, wherein the devices according to the invention are electroluminescent devices.

[0037] In the display device, the at least two electroluminescent devices may share at least one semiconducting layer comprising the coordination complex.

[0038] The object is further achieved by a method for manufacturing an electronic device or a display device as defined herein, the method comprising the steps: (1) evaporating the coordination complex defined herein, and (2) Deposition of the vapor of the coordination complex onto a solid support. In the process of the invention, the evaporation and deposition may each comprise co-evaporation and co-deposition of the coordination complex with a matrix material.

[0039] The object is further achieved by a semiconducting material comprising a hole transport matrix material and a p-dopant, wherein the p-dopant is the coordination complex defined herein.

[0040] Finally, the task is solved by a coordination complex which comprises at least one electropositive atom M and at least one anionic methide ligand L, represented by the following formula (I):wherein A 1 and A 2 each independently from C1 to C 30 - perfluorinated sulfonyl, A 3 from C6 to C 30 - perfluorinated sulfonyl, and M is selected from the group consisting of a) Be, Sr, Ba, Mn, Fe, Co, Ni, Cd, Sn, Pb, each in the oxidation state (II), or which is represented by one of the following formulas

[0041] In certain embodiments, this coordination complex, as defined above, may be restricted with respect to one or more aspects thereof.

[0042] With respect to the coordination complex defined herein, it may be assumed that the lithium complex comprising tris(trifluoromethylsulfonyl)methide, ie compound E1, is excluded from the scope thereof. Additional layers

[0043] According to the invention, the electronic device may comprise further layers in addition to the layers already mentioned. Exemplary embodiments of the respective layers are described below. carrier

[0044] The substrate can be any substrate commonly used in the manufacture of electronic devices, such as organic light-emitting diodes. If light is to be emitted through the substrate, the substrate must be a transparent or semi-transparent material, for example, a glass substrate or a transparent plastic substrate. If light is to be emitted through the top surface, the substrate can be either a transparent or non-transparent material, for example, a glass substrate, a plastic substrate, a metal substrate, or a silicon substrate. anode electrode

[0045] Either the first electrode or the second electrode can be an anode electrode. The anode electrode can be formed by depositing or sputtering a material used to form the anode electrode. The material used to form the anode electrode can be a high work function material to facilitate hole injection. The anode material can also be selected from low work function materials (e.g., aluminum). The anode electrode can be a transparent or reflective electrode. Transparent conductive oxides such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2), aluminum zinc oxide (AlZO), and zinc oxide (ZnO) can be used to form the anode electrode. The anode electrode can also be formed using metals, typically silver (Ag), gold (Au), or metal alloys. Hole injection layer

[0046] In accordance with the invention, the hole injection layer may comprise the coordination complex described in detail above.

[0047] The hole injection layer (HIL) can be formed on the anode electrode by vacuum deposition, spin coating, printing, casting, slot die coating, Langmuir-Blodgett (LB) coating, or similar. When the HIL is formed using vacuum deposition, the deposition conditions may vary depending on the compound used to form the HIL and the desired structure and thermal properties of the HIL. However, the typical vacuum deposition conditions include a deposition temperature of 100°C to 500°C, a pressure of 10 -8 up to 10 -3 Torr (1 Torr corresponds to 133.322 Pa) and a deposition rate of 0.1 to 10 nm / sec.

[0048] When the HIL is formed using spin coating or printing, the conditions can vary depending on the compound used to form the HIL and the desired structure and thermal properties of the HIL. For example, the coating conditions can include a coating speed of about 2000 rpm to about 5000 rpm and a heat treatment temperature of about 80°C to about 200°C. Heat treatment removes any solvent after the coating is complete.

[0049] The HIL can be formed from any compound commonly used to form an HIL, particularly if the electronic device comprises a layer other than the one comprising the coordination complex. Examples of compounds that can be used to form the HIL include a phthalocyanine compound such as copper phthalocyanine (CuPc), 4,4',4''-tris(3-methylphenylphenylamino)triphenylamine (m-MTDATA), TDATA, 2T-NATA, polyaniline / dodecylbenzenesulfonic acid (Pani / DBSA), poly(3,4-ethylenedioxythiophene) / poly(4-styrenesulfonate) (PEDOT / PSS), polyaniline / camphorsulfonic acid (Pani / CSA), and polyaniline / poly(4-styrenesulfonate) (PANI / PSS).

[0050] In such a case, the HIL can be a pure layer of p-dopant or can be selected from a p-dopant-doped hole-transport matrix compound. Common examples of known redox-doped hole-transport materials are: copper phthalocyanine (CuPc), whose HOMO level is approximately -5.2 eV, doped with tetrafluorotetracyanoquinonimethane (F4TCNQ), whose LUMO level is approximately -5.2 eV; zinc phthalocyanine (ZnPc) (HOMO = -5.2 eV) doped with F4TCNQ; α-NPD (N,N'-bis(naphthalen-1-yl)-N,N'-bis(phenyl)benzidine) doped with F4TCNQ; and α-NPD doped with 2,2'-(perfluoronaphthalene-2,6-diylidene) dimalonitrile (PD1). α-NPD doped with 2,2',2"-(cyclopropane-1,2,3-triylidene)tris(2-(p-cyanotetrafluorophenyl)acetonitrile) (PD2). The dopant concentrations can be chosen between 1 and 20 wt%, preferably between 3 wt% and 10 wt%.

[0051] The thickness of the HIL can be in the range of about 1 nm to about 100 nm, for example, from about 1 nm to about 25 nm. When the thickness of the HIL is in this range, the HIL can have excellent hole-injection properties without a substantial penalty in operating voltage. Hole transport layer

[0052] According to the invention, the hole transport layer may comprise the coordination complex as described in detail above.

[0053] The hole-transport layer (HTL) can be formed by vacuum deposition, spin coating, printing, casting, slot-die coating, Langmuir-Blodgett (LB) coating, or similar methods. When forming the HTL using vacuum deposition or spin coating, the deposition conditions can be similar to those for forming the HIL. However, the conditions for vacuum or solution deposition may vary depending on the compound used to form the HTL.

[0054] In the case where the HTL does not comprise the coordination complex according to the invention, but the coordination complex is comprised in another layer, the HTL can be formed by a compound commonly used to form an HTL. Suitable compounds are disclosed, for example, in Yasuhihiko Shirota and Hiroshi Kageyama, Chem. Rev. 2007, 107, 953-1010 and incorporated by reference. Examples of the compound that can be used to form the HTL are: carbazole derivatives, such as N-phenylcarbazole or polyvinylcarbazole; benzidine derivatives, such as N,N'-bis(3-methylphenyl)-N,N'-diphenyl-[1,1-biphenyl]-4,4'-diamine (TPD), or N,N'-di(naphthalen-1-yl)-N,N'-diphenylbenzine (alpha-NPD); and a triphenylamine-based compound such as 4,4',4"-tris(N-carbazolyl)triphenylamine (TCTA). Among these compounds, TCTA can transport holes and prevent excitons from diffusing into the EML.

[0055] The thickness of the HTL may be in the range of about 5 nm to about 250 nm, preferably about 10 nm to about 200 nm, further about 20 nm to about 190 nm, further about 40 nm to about 180 nm, further about 60 nm to about 170 nm, further about 80 nm to about 160 nm, further about 100 nm to about 160 nm, further about 120 nm to about 140 nm. A preferred thickness of the HTL may be 170 nm to 200 nm.

[0056] When the thickness of the HTL is in this range, the HTL can exhibit excellent hole transport properties without a substantial penalty in operating voltage. Electron-blocking layer

[0057] The function of the electron-blocking layer (EBL) is to prevent electrons from transferring from the emitting layer to the hole-transporting layer, thereby confining electrons to the emitting layer. This improves efficiency, operating voltage, and / or lifetime. Typically, the electron-blocking layer comprises a triarylamine compound. The triarylamine compound can have a LUMO level that is closer to vacuum than the LUMO level of the hole-transporting layer. The electron-blocking layer can have a HOMO level that is farther from vacuum than the HOMO level of the hole-transporting layer. The thickness of the electron-blocking layer can be selected between 2 and 20 nm.

[0058] The electron-blocking layer may comprise a compound of the formula Z below (Z)

[0059] In formula Z, CY1 and CY2 are the same or different from each other and each independently represents a benzene cycle or a naphthalene cycle, Ar1 to Ar3 are the same or different from each other and each independently selected from the group consisting of hydrogen; a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; and a substituted or unsubstituted heteroaryl group having 5 to 30 carbon atoms, Ar4 is selected from the group consisting of a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted triphenylene group and a substituted or unsubstituted heteroaryl group having 5 to 30 carbon atoms, L is a substituted or unsubstituted arylene group having 6 to 30 carbon atoms.

[0060] If the electron-blocking layer has a high triplet level, it can also be called a triplet control layer.

[0061] The function of the triplet control layer is to reduce the quenching of triplets when a phosphorescent green or blue emitting layer is used. This allows higher light emission efficiency from a phosphorescent emitting layer to be achieved. The triplet control layer is selected from triarylamine compounds with a triplet level above the triplet level of the phosphorescent emitter in the adjacent emitting layer. Suitable compounds for the triplet control layer, in particular the triarylamine compounds, are described in EP 2 722 908 A1. Emission layer (EML)

[0062] The EML can be formed on the HTL by vacuum deposition, spin coating, slot die coating, printing, casting, LB deposition, or similar. When the EML is formed using vacuum deposition or spin coating, the deposition conditions can be similar to those used to form the HIL. However, the deposition and coating conditions can vary depending on the compound used to form the EML.

[0063] The emitting layer can be formed from a combination of a host and an emitter dopant. Examples of the host are Alq3, 4,4'-N,N'-dicarbazole-biphenyl (CBP), poly(n-vinylcarbazole) (PVK), 9,10-di(naphthalen-2-yl)anthracene (ADN), 4,4',4"-tris(carbazol-9-yl)triphenylamine (TCTA), 1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene (TPBI), 3-tert-butyl-9,10-di-2-naphthylanthracene (TBADN), distyrylarylene (DSA), bis(2-(2-(2-hydroxyphenyl)benzothiazolate)zinc (Zn(BTZ)2), G3 below, Compound 1 below, and Compound 2 below.

[0064] The emitter dopant can be a phosphorescent or fluorescent emitter. Phosphorescent emitters and emitters that emit light via a thermally activated delayed fluorescence (TADF) mechanism may be preferred due to their higher efficiency. The emitter can be a small molecule or a polymer.

[0065] Examples of red emitter dopants include, but are not limited to, PtOEP, Ir(piq)3, and Btp2Ir(acac). These compounds are phosphorescent emitters, but red-emitting fluorescent dopants can also be used.

[0066] Examples of phosphorescent green emitter dopants are Ir(ppy)3 (ppy = phenylpyridine), Ir(ppy)2(acac), and Ir(mpyp)3, shown below. Compound 3 is an example of a fluorescent green emitter, and its structure is shown below.

[0067] Examples of phosphorescent blue emitter dopants are F2Irpic, (F2ppy)2Ir(tmd), and Ir(dfppz)3, ter-fluorene; the structures are shown below. 4,4'-Bis(4-diphenylamiostyryl)biphenyl (DPAVBi), 2,5,8,11-tetra-tert-butylperylene (TBPe), and compound 4 are examples of fluorescent blue emitter dopants.

[0068] The amount of emitter dopant can range from about 0.01 to about 50 parts by weight, based on 100 parts by weight of the host. Alternatively, the emitting layer can be made of a light-emitting polymer. The EML can have a thickness of about 10 nm to about 100 nm, for example, from about 20 nm to about 60 nm. When the thickness of the EML is in this range, the EML can have excellent light emission without a substantial penalty in operating voltage. Hole-blocking layer (HBL)

[0069] A hole-blocking layer (HBL) can be formed on the EML using vacuum deposition, spin coating, slot die coating, printing, casting, LB deposition, or similar techniques to prevent the diffusion of holes into the ETL. If the EML contains a phosphorescent dopant, the HBL can also have a triplet exciton-blocking function.

[0070] When the HBL is formed using vacuum deposition or spin coating, the deposition conditions can be similar to those for forming the HIL. However, the deposition and coating conditions can vary depending on the compound used to form the HBL. Any compound commonly used to form an HBL can be used. Examples of compounds for forming the HBL include oxadiazoline derivatives, triazole derivatives, and phenanthroline derivatives.

[0071] The HBL may have a thickness in the range of about 5 nm to about 100 nm, for example, from about 10 nm to about 30 nm. When the thickness of the HBL is in this range, the HBL can have excellent hole-blocking properties without a substantial penalty in operating voltage. Electron transport layer (ETL)

[0072] The OLED according to the present invention may contain an electron transport layer (ETL).

[0073] According to different embodiments, the OLED may comprise an electron transport layer or an electron transport layer stack comprising at least a first electron transporting sub-layer and at least a second electron transporting sub-layer.

[0074] By appropriately adjusting the energy levels of specific layers of the ETL, electron injection and transport can be controlled and holes can be effectively blocked. This can extend the lifespan of the OLED.

[0075] The electron-transport layer of the electronic device may comprise an organic electron-transport matrix material (ETM). Furthermore, the electron-transport layer may comprise one or more n-dopants. Suitable compounds for the ETM are not particularly limited. According to one embodiment, the electron-transport matrix compound consists of covalently bonded atoms. Preferably, the electron-transport matrix compound comprises a conjugated system of at least 6, more preferably at least 10, delocalized electrons. In one embodiment, the conjugated system may be comprised of delocalized electrons in aromatic or heteroaromatic structural units, as disclosed, for example, in documents EP 1 970 371 A1 or WO 2013 / 079217 A1.

[0076] According to one embodiment, the electron-transport layer may be electrically doped with an n-type electrical dopant. According to another embodiment, the electron-transport layer may comprise the second electron-transporting sublayer, which is arranged closer to the cathode than the first electron-transporting sublayer, and only the second electron-transporting sublayer may comprise the n-type electrical dopant.

[0077] The electrical n-dopant may be selected from electropositive elemental metals and / or metal salts and metal complexes of electropositive metals, in particular from elemental forms, salts and / or complexes of metals selected from alkali metals, alkaline earth metals and rare earth metals. Electron injection layer (EIL)

[0078] The optional EIL, which can facilitate the injection of electrons from the cathode, can be formed on the ETL, preferably directly on the electron-transport layer. Examples of materials for forming the EIL include lithium 8-hydroxyquinolinolate (LiQ), LiF, NaCl, CsF, Li2O, BaO, Ca, Ba, Yb, and Mg, which are known in the art. The deposition and coating conditions for forming the EIL are similar to those for forming the HIL; however, the deposition and coating conditions can vary depending on the material used to form the EIL.

[0079] The thickness of the EIL may be in the range of about 0.1 nm to about 10 nm, for example, in the range of about 0.5 nm to about 9 nm. When the thickness of the EIL is in this range, the EIL can have satisfactory electron-injecting properties without a substantial penalty in operating voltage. cathode electrode

[0080] The cathode electrode is formed on the EIL, if present. The cathode electrode may be formed from a metal, an alloy, an electrically conductive compound, or a mixture thereof. The cathode electrode may have a low work function. For example, the cathode electrode may be formed from lithium (Li), magnesium (Mg), aluminum (Al), aluminum (Al)-lithium (Li), calcium (Ca), barium (Ba), ytterbium (Yb), magnesium (Mg)-indium (In), magnesium (Mg)-silver (Ag), or the like. Alternatively, the cathode electrode may be formed from a transparent conductive oxide such as ITO or IZO.

[0081] The thickness of the cathode electrode may be in the range of about 5 nm to about 1000 nm, for example, in the range of about 10 nm to about 100 nm. When the thickness of the cathode electrode is in the range of about 5 nm to about 50 nm, the cathode electrode may be transparent or semi-transparent even if it is formed of a metal or a metal alloy.

[0082] It should be understood that the cathode electrode is not part of an electron injection layer or the electron transport layer. Charge-generating layer / hole-generating layer

[0083] The charge-generating layer (CGL) may consist of a double layer. If the charge-generating layer is a p-type charge-generating layer (hole-generating layer), it may comprise the coordination complex defined herein.

[0084] Typically, the charge-generating layer is a pn junction, which combines an n-type charge-generating layer (electron-generating layer) and a hole-generating layer. The n-side of the pn junction generates electrons and injects them into the adjacent layer toward the anode. Similarly, the p-side of the pn junction generates holes and injects them into the adjacent layer toward the cathode.

[0085] Charge-generating layers are used in tandem devices, for example, in tandem OLEDs, which comprise two or more emitting layers between two electrodes. In a tandem OLED comprising two emitting layers, the n-type charge-generating layer provides electrons to the first light-emitting layer, which is located adjacent to the anode, while the hole-generating layer provides holes to the second light-emitting layer, which is located between the first emitting layer and the cathode.

[0086] According to the invention, it can be assumed that the electronic device comprises a hole-injection layer and a hole-generating layer. If a layer other than the hole-generating layer comprises the coordination complex defined herein, it is not mandatory for the hole-generating layer to also comprise the coordination complex defined herein. In such a case, the hole-generating layer can consist of an organic matrix material doped with a p-type dopant. Suitable matrix materials for the hole-generating layer can be materials that are commonly used as hole-injection and / or hole-transport matrix materials. The p-type dopant used for the hole-generating layer can also use conventional materials.For example, the p-dopant can be selected from a group consisting of tetrafluoro-7,7,8,8,8-tetracyanoquinodimethane (F4-TCNQ), derivatives of tetracyanoquinodimethane, radialene derivatives, iodine, FeCl3, FeF3, and SbCl5. Furthermore, the host can be one selected from a group consisting of N,N'-di(naphthalen-1-yl)-N,N-diphenylbenzidine (NPB), N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1-biphenyl-4,4'-diamine (TPD), and N,N',N'-tetranaphthylbenzidine (TNB).

[0087] According to one embodiment, the hole-generating layer comprised the coordination complex defined herein as detailed above.

[0088] The n-type charge-generating layer may be a layer of a pure n-dopant, for example, an electropositive metal, or may consist of an organic matrix material doped with the n-dopant. According to one embodiment, the n-type dopant may be an alkali metal, alkali metal compound, alkaline earth metal, or alkaline earth metal compound. According to another embodiment, the metal may be one selected from a group consisting of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, La, Ce, Sm, Eu, Tb, Dy, and Yb. In particular, the n-dopant may be one selected from a group consisting of Cs, K, Rb, Mg, Na, Ca, Sr, Eu, and Yb. Suitable matrix materials for the electron-generating layer may be materials that are commonly used as matrix materials for electron injection or electron transport layers.The matrix material may, for example, be one selected from a group consisting of ophthalic triazine compounds, hydroxyquinoline derivatives such as tris(8-hydroxyquinoline)aluminum, benzazole derivatives and silole derivatives.

[0089] According to one embodiment, the n-type charge-generating layer may contain a compound of the following chemical formula X, wherein each of A1 to A6 is hydrogen, a halogen atom, nitrile (-CN), nitro (-NO2), sulfonyl (-SO2R), sulfoxide (-SOR), sulfonamide (-SO2NR), sulfonate (-SO3R), trifluoromethyl (-CF3), ester (-COOR), amide (-CONHR or -CONRR'), substituted or unsubstituted straight-chain or branched-chain C1-C12 alkoxy, substituted or unsubstituted straight-chain or branched-chain C1-C12 alkyl, substituted or unsubstituted straight-chain or branched-chain C2-C12 alkenyl, substituted or unsubstituted aromatic or non-aromatic hetero ring, substituted or unsubstituted aryl, substituted or unsubstituted mono- or di-arylamine, substituted or unsubstituted arylalkylamine or the like.Each of the above R's herein may be substituted or unsubstituted C1-C60 alkyl, substituted or unsubstituted aryl, or a substituted or unsubstituted 5- to 7-membered hetero ring or the like.

[0090] An example of such an n-type charge-generating layer can be a layer comprising CNHAT. The hole-generating layer is arranged on top of the n-type charge-generating layer. Organic light-emitting diode (OLED)

[0091] According to one aspect of the present invention, there is provided an organic light-emitting diode (OLED) comprising: a substrate; an anode electrode formed on the substrate, a hole injection layer, a hole transport layer, an electron blocking layer, an emitting layer, a hole blocking layer, and a cathode electrode.

[0092] According to another aspect of the present invention, there is provided an organic light-emitting diode (OLED) comprising: a substrate; an anode electrode formed on the substrate, a hole injection layer, a hole transport layer, an electron blocking layer, an emitting layer, a hole blocking layer, and a cathode electrode.

[0093] According to another aspect of the present invention, there is provided an organic light-emitting diode (OLED) comprising: a substrate; an anode electrode formed on the substrate, a hole injection layer, a hole transport layer, an electron blocking layer, an emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a cathode electrode.

[0094] According to different embodiments of the present invention, OLEDs can be provided which comprise layers arranged between the above-mentioned layers, on the carrier or on the top electrode.

[0095] According to one aspect, the OLED may comprise a layered structure comprising a carrier arranged adjacent to an anode electrode, the anode electrode being arranged adjacent to a first hole injection layer, the first hole injection layer being arranged adjacent to a first hole transport layer, the first hole transport layer being arranged adjacent to a first electron blocking layer, the first electron blocking layer being arranged adjacent to a first emission layer, the first emission layer being arranged adjacent to a first electron transport layer, the first electron transport layer being arranged adjacent to a first n-type charge generating layer, the n-type charge generating layer being arranged adjacent to a hole generating layer, the hole generating layer being arranged adjacent to a second hole transport layer, the second hole transport layer being arranged adjacent to a second electron blocking layer,the second electron-blocking layer is arranged next to a second emission layer, and an optional electron-transport layer and / or an optional injection layer is arranged between the second emission layer and the cathode electrode.

[0096] For example, the OLED can be Fig. 2 be formed by a method wherein on a carrier (110), an anode (120), a hole injection layer (130), a hole transport layer (140), an electron blocking layer (145), an emission layer (150), a hole blocking layer (155), an electron transport layer (160), an electron injection layer (180) and the cathode electrode (190) are formed successively in this order. Details and definitions of the invention

[0097] The electronic device according to the present invention comprises at least one (semiconducting) layer, which may comprise a charge transport matrix compound and the coordination complex. The coordination complex may be embedded in the matrix material, i.e., the matrix material is the predominant material in such a layer. Likewise, it may be provided that the matrix material and the dopant in the semiconducting layer are separated from one another into a first sublayer comprising the matrix material and a second sublayer comprising the dopant, or, in a preferred embodiment, each consist of these. Likewise, it may be provided that the layer consists of the coordination complex.

[0098] After deposition, the coordination complex can diffuse into the adjacent layers, in particular the coordination complex can diffuse into the layer onto which it is deposited.

[0099] Alternatively or additionally, the coordination complex of the present invention may comprise another anionic ligand and / or an electrically neutral ligand.

[0100] The electronic device described herein may be an electronic device based on semiconducting layers. In particular, the hole injection layer, the hole transport layer, and the hole generation layer are semiconducting layers.

[0101] It is understood that in coordination complexes, at least one ligand is bound to the metal cation by at least one coordinate bond. In this context, it is understood that the coordination bond is predominantly covalent in nature. The ligand that forms the coordinate bond to the metal cation can be the anionic ligand.

[0102] A “methide” in the sense of the present invention is a carbanion with the general formula CR3 - .

[0103] The term “hydrocarbyl group” as used herein should be understood to include any organic group containing carbon atoms, in particular organic groups such as alkyl, aryl, heteroaryl, heteroalkyl, in particular those groups which are common substituents in organic electronics.

[0104] As used herein, the term "alkyl" is intended to encompass both linear and branched alkyl and cyclic alkyl. For example, C3 alkyl can be selected from n-propyl and isopropyl. Likewise, C4 alkyl includes n-butyl, sec-butyl, and t-butyl. Likewise, C6 alkyl includes n-hexyl and cyclohexyl.

[0105] The subscript number n in C n refers to the total number of carbon atoms in the respective alkyl, arylene, heteroarylene or aryl group.

[0106] The term "aryl" as used herein is intended to include phenyl (C6-aryl), fused aromatics such as naphthalene, anthracene, phenanthrene, tetracene, etc. Also included are biphenyl and oligo- or polyphenyls such as terphenyl, etc. Also included are all other aromatic hydrocarbon substituents such as fluorenyl, etc. Arylene or heteroarylene refers to groups to which two additional units are attached.

[0107] The term “heteroaryl” as used herein refers to aryl groups in which at least one carbon atom is substituted by a heteroatom, preferably selected from N, O, S, B or Si.

[0108] The term "halogenated" refers to an organic compound in which one hydrogen atom is replaced by a halogen atom. The term "perhalogenated" refers to an organic compound in which all hydrogen atoms are replaced by halogen atoms. The meaning of the terms "fluorinated" and "perfluorinated" is analogous.

[0109] The term “acyl” as used herein refers to a functional group having the general structure R-(C=O)-, where R is alkyl, aryl or a corresponding heteroatom-containing group.

[0110] The term “sulfonyl” as used herein refers to a functional group having the general structure R'-(SO2)-, where R' is alkyl, aryl or a corresponding heteroatom-containing group.

[0111] The term "phosphoryl" as used herein refers to a functional group having the general structure R"1R"2(P=O)- where R"1 and R"2 are independently alkyl, aryl or a corresponding heteroatom-containing group.

[0112] The subscript number n in C n -Heteroaryl refers only to the number of carbon atoms, excluding the number of heteroatoms. In this context, it is clear that a C3-heteroarylene group is an aromatic compound containing three carbon atoms, such as pyrazole, imidazole, oxazole, thiazole, and the like.

[0113] For the purposes of the invention, the term "between" with respect to a layer located between two other layers does not exclude the presence of further layers that may be disposed between one layer and one of the other two layers. For the purposes of the invention, the term "in direct contact" with respect to two layers that are in direct contact with each other means that no further layers are disposed between these two layers. A layer deposited on the other layer is considered to be in direct contact with this layer.

[0114] In the context of the present description, the term "substantially non-emissive" or "non-emissive" means that the contribution of the compound or layer to the visible emission spectrum of the device is less than 10%, preferably less than 5%, relative to the visible emission spectrum. The visible emission spectrum is an emission spectrum with a wavelength of about ≥ 380 nm to about ≤ 780 nm.

[0115] Preferably, the organic semiconducting layer comprising at least one electrical dopant is substantially non-emissive or non-emissive.

[0116] With respect to the electronic device according to the invention, the compounds mentioned in the experimental part may be most preferred.

[0117] The electronic device according to the invention may be an organic electroluminescent device (OLED), an organic photovoltaic device (OPV) or an organic field effect transistor (OFET).

[0118] According to another aspect, the organic electroluminescent device according to the present invention may comprise more than one emission layer, preferably two or three emission layers. An OLED comprising more than one emission layer is also referred to as a tandem OLED or stacked OLED.

[0119] The organic electroluminescent device (OLED) can be a bottom-emitting or top-emitting device.

[0120] Another aspect is directed to a device comprising at least one organic electroluminescent device (OLED). A device comprising organic light-emitting diodes is, for example, a display or a lighting panel.

[0121] In this specification, the following defined terms shall be used as the definitions unless another definition is given in the claims or elsewhere in the specification.

[0122] In the context of this description, the term “different” or “differentiated” in connection with the matrix material means that the matrix material is different in its structural formula.

[0123] The energy levels of the highest occupied molecular orbital, also called HOMO, and the lowest unoccupied molecular orbital, also called LUMO, are measured in electronvolts (eV).

[0124] The terms "OLED" and "organic light-emitting diode" are used interchangeably and have the same meaning. The term "organic electroluminescent device" as used herein can include both organic light-emitting diodes and organic light-emitting transistors (OLETs).

[0125] As used herein, "weight percent", "wt%", wt%, "percent weight", "% weight" and variations thereof refer to a composition, component, substance or agent as the weight of that component, substance or agent of the respective electron transport layer divided by the total weight of the respective electron transport layer thereof and multiplied by 100. It is understood that the total weight percentage of all components, substances and agents of the respective electron transport layer and electron injection layer is selected so as not to exceed 100 wt%.

[0126] As used herein, "volume percent", "vol%", "vol%", "percent volume", "% volume" and variations thereof refer to a composition, component, substance or agent as the volume of that component, substance or agent of the respective electron transport layer divided by the total volume of the respective electron transport layer thereof and multiplied by 100. It is understood that the total volume percentage of all components, substances and agents of the cathode layer is selected so as not to exceed 100 vol%.

[0127] All numerical values ​​herein are interpreted as modified by the term "about," whether expressly stated or not. As used herein, the term "about" refers to the variation in numerical magnitude that may occur. Whether or not modified by the term "about," the claims include equivalents to the amounts.

[0128] It should be noted that, as used in this specification and the appended claims, the singular forms "a", "an", and "the" include plural referents unless the content clearly dictates otherwise.

[0129] The terms "free from," "does not contain," or "does not comprise" do not exclude impurities. Impurities have no technical effect on the object achieved by the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0130] These and / or other aspects and advantages of the present invention will become apparent and more readily appreciated from the following description of exemplary embodiments taken in conjunction with the accompanying drawings: Fig. 1 is a schematic sectional view of an organic light-emitting diode (OLED) according to an exemplary embodiment of the present invention; Fig. 2 is a schematic sectional view of an OLED according to an exemplary embodiment of the present invention. Fig. 3 is a schematic cross-sectional view of a tandem OLED including a charge generating layer according to an exemplary embodiment of the present invention. EMBODIMENTS OF THE INVENTIONAL DEVICE

[0131] Reference will now be made in detail to the exemplary embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to like elements throughout. The exemplary embodiments will now be described to explain aspects of the present invention with reference to the figures.

[0132] Herein, when a first element is referred to as being formed or disposed "on" a second element, the first element may be disposed directly on the second element, or one or more other elements may be disposed therebetween. When a first element is referred to as being formed or disposed "directly on" a second element, no other elements are disposed therebetween.

[0133] Fig. 1 is a schematic cross-sectional view of an organic light-emitting diode (OLED) 100 according to an exemplary embodiment of the present invention. The OLED 100 includes a carrier 110, an anode 120, a hole injection layer (HIL) 130, a hole transport layer (HTL) 140, an emission layer (EML) 150, and an electron transport layer (ETL) 160. The electron transport layer (ETL) 160 is formed directly on the EML 150. An electron injection layer (EIL) 180 is disposed on the electron transport layer (ETL) 160. The cathode 190 is disposed directly on the electron injection layer (EIL) 180.

[0134] Instead of a single electron transport layer 160, an electron transport layer stack (ETL) can optionally be used.

[0135] Fig. 2 is a schematic sectional view of an OLED 100 according to another exemplary embodiment of the present invention. Fig. 2 differs from Fig. 1 because the OLED 100 of Fig. 2 comprises an electron blocking layer 145 and a hole blocking layer (HBL) 155.

[0136] With reference to Fig. 2, the OLED 100 includes a carrier 110, an anode 120, a hole injection layer (HIL) 130, a hole transport layer (HTL) 140, an electron blocking layer (EBL) 145, an emission layer (EML) 150, a hole blocking layer (HBL) 155, an electron transport layer (ETL) 160, an electron injection layer (EIL) 180, and a cathode electrode 190.

[0137] Fig. 3 is a schematic sectional view of a tandem OLED 200 according to another exemplary embodiment of the present invention. Fig. 3 differs from Fig. 2 because the OLED 100 of Fig. 3 further comprises a charge generating layer and a second emission layer.

[0138] With reference to Fig. 3, the OLED 200 includes a carrier 110, an anode 120, a first hole injection layer (HIL) 130, a first hole transport layer (HTL) 140, a first electron blocking layer (EBL) 145, a first electron transport layer (ETL) 160, an n-type charge generation layer (n-type CGL) 185, a hole generation layer (p-type charge generation layer; p-type GCL) 135, a second hole transport layer (HTL) 141, a second electron blocking layer (EBL) 146, a second emission layer (EML) 151, a second hole blocking layer (EBL) 156, a second electron transport layer (ETL) 161, a second electron injection layer (EIL) 181, and a cathode 190.

[0139] Although in Fig. 1, Fig. 2 and Fig. 3, a sealing layer may be formed on the cathode electrodes 190 to seal the OLEDs 100 and 200. Furthermore, various other modifications may be made.

[0140] One or more exemplary embodiments of the present invention will now be described in detail with reference to the following examples. However, these examples are not intended to limit the purpose and scope of the one or more exemplary embodiments of the present invention. EXPERIMENTAL PART A. Preparation of methanide coordination complexes

[0141] Methanide complexes for device testing can be prepared from commercially available conjugate acids using known generic methods described in the following literature: EP 1 344 772 A1 (D1); Inorganic Chemistry 1988, 27, 2135-2137 (D2); Journal of Organic Chemistry 1998, 64, 2910-2913 (D3); Synlett 1999 (12), 1990-1992 (D4); Tetrahedron 2002, 58, 3835-3840 (D5).

[0142] 1-(Bis((trifluoromethyl)sulfonyl)methyl)-2,3,5,6-tetrafluoro-4-(trifluoromethyl)benzene, a new acid which served as starting material for the preparation of compounds E9, E13, E14 and E15, was prepared in two steps: a) 1,2,4,5-Tetrafluoro-3-(trifluoromethyl)-6-(((trifluoromethyl)sulfonyl)methyl)benzene

[0143] To a solution of 2.9 mL of methyltriflon in 80 mL of Et2O, stirred in a cooling bath at -80°C under N2, 19 mL (32 mmol) of a 1.7M t-BuLi solution in pentane was slowly added. After 30 minutes of continuous stirring, 4.1 mL (6.8 g / 29 mmol) of 1,2,3,4,5-pentafluoro-6-(trifluoromethyl)benzene (perfluorotoluene) was added, and the mixture was stirred overnight at RT.

[0144] The reaction was quenched by adding 100 mL of water and stirring for 30 min. The organic phase was separated, washed, and dried with MgSO4. Removal of the solvent in vacuo yielded 4.51 g (43%) of product as white crystals. b) 1-(Bis((trifluoromethyl)sulfonyl)methyl)-2,3,5,6-tetrafluoro-4-(trifluoromethyl)benzene

[0145] To 4.5 g of the intermediate prepared in the previous step, dissolved in 200 mL of Et2O, and stirred in a cooling bath at -80°C under N2, 7.3 mL of 1.7M t-BuLi in pentane was added. The mixture was stirred for 1 hour and cooled again. Then, 2.26 mL of trifluoromethanesulfonic anhydride was slowly added. After 30 minutes of continuous stirring at -80°C, 7.3 mL of 1.7M t-BuLi in pentane was slowly added to the stirred mixture with continuous cooling, and the mixture was allowed to stir and warm overnight.

[0146] The reaction was quenched by adding 100 mL of water and stirring for 30 min. The organic phase was separated, washed, and dried with Na2SO4. The crude product obtained as a wax was purified by short-path sublimation at 120 °C, yielding 3.2 g (55%) of colorless crystals.

[0147] Surprisingly, it was found that complexes E9, E13, E14 and E15 and analogous complexes E4, E23, E24 and E25 can also be purified by preparative sublimation, making these compounds suitable for device preparation by VTE. Exemplary representation of coordination complexes (tris((trifluoromethyl)sulfonyl)methyl)lithium (E1)

[0148] To a stirred solution of 2.72 g (6.6 mmol) of CH acid (purchased from Synquest Labs) in 15 mL of MTBE, 55.4 mg (1.05 eq.) of LiH was added. After hydrogen evolution ceased, the mixture was evaporated to dryness and further dried by adding toluene and repeating the vacuum evaporation at least once. Yield: 2.29 g (84%) ((perfluorophenyl)bis(trifluoromethyl)sulfonyl)methyl)lithium (E4)

[0149] A precisely weighed amount of LiH (26.3 mg / 1 eq.) was added to a stirred solution of 1.465 g of CH acid (purchased from Manchester Organics) in MTBE (10 mL). After hydrogen evolution had ceased, the resulting clear solution was evaporated to dryness. The residue was further dried under vacuum at 50°C. Yield: 1.25 g (84%) white powder. B. Device experiments

[0150] The formulas of the carrier materials listed below are as follows: F1, used as hole-transporting matrix in VTE-engineered layers, is biphenyl-4-yl(9,9-diphenyl-9H-fluoren-2-yl)-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-amine, CAS 1242056-42-3; F2, used as a hole transport matrix in solution-processed films, is (poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(4,4'-(N-(4-sec-butylphenyl)diphenylamine)], commercially available from Solaris Chem Inc); F3 is (3-(Dibenzo[c,h]acridin-7-yl)phenyl)diphenylphosphine oxide, CAS 1440545-22-1; F4 is N,N-bis(4-(dibenzo[b,d]furan-4-yl)phenyl)-[1,1':4',1"-terphenyl]-4-amine, CAS 1198399-61-9; F5 is 2,4-diphenyl-6-(4',5',6'-triphenyl-[1,1':2',1":3",1"':3'",1"x. "xm"-quinquephenyl]-3'"-yl)-1,3,5-triazine, CAS 2032364-64-8; F6 is diphenyl(3'-(10-phenylanthracen-9-yl)-[1,1'-biphenyl]-4-yl)phosphine oxide, CAS 2138371-45-4; F7 is 8-(4-(4,6-di(naphthalen-2-yl)-1,3,5-triazin-2-yl)phenyl)quinolone, CAS 1312928-44-1; ND2 is lithium tetra(1H-pyrazol-1-yl)borate, CAS 14728-62-2; LiQ is lithium 8-hydroxyquinolinolate, CAS 850918-68-2;

[0151] ABH-113 and H09 are emitter hosts and NUBD-370 and BD-200 are blue fluorescent emitter dopants, commercially available from SFC, Korea.

[0152] ITO is indium tin oxide.

[0153] In the experiments, LiTFSI (Compound B2, CAS 90076-65-6), disclosed in WO2017 / 029370 and WO2017 / 029366 as a hole-injecting material and / or p-dopant, was used as a reference material. STANDARD PROCEDURE Voltage stability

[0154] OLEDs are powered by constant-current circuits. These circuits can deliver a constant current over a specific voltage range. The wider the voltage range, the greater the power losses of such devices. Therefore, the change in operating voltage during operation must be minimized.

[0155] The operating voltage of an OLED is temperature-dependent. Therefore, the voltage stability must be assessed at thermal equilibrium. Thermal equilibrium is reached after one hour of operation.

[0156] Voltage stability is measured by measuring the difference in operating voltage after 50 hours and after 1 hour of operation at a constant current density. A current density of 30 mA / cm 2 used. The measurements are carried out at room temperature. dU[V]=U(50 h, 30 mA / cm2)−U(1 h, 30 mA / cm2) Efficiency evaluation

[0157] To test the performance of the inventive examples compared to the prior art, the current efficiency is measured at 20 °C. The current-voltage characteristics are determined using a Keithley 2635 Source Measure Unit by sourcing a voltage in V and measuring the current in mA flowing through the device under test conditions. The voltage applied to the device is varied in steps of 0.1 V in the range between 0 V and 10 V. Likewise, the luminance-voltage characteristics and CIE coordinates are determined by measuring the luminance in cd / m2 Using an Instrument Systems CAS-140CT array spectrometer calibrated by the German Accreditation Body (DAkkS), the cd / A efficiency is measured for each voltage. The cd / A efficiency at 10 mA / cm2 is determined by interpolating the respective luminance-voltage and current-voltage characteristics. Glass transition temperature

[0158] The glass transition temperature is determined under nitrogen and using a heating rate of 10 K per minute in a Mettler Toledo DSC 822e differential scanning calorimeter as described in DIN EN ISO 11357 published in March 2010. Examples

[0159] 1) Using a mehide coordination complex as a pure hole injection layer in a blue OLED

[0160] Table 1a describes the model device schematically. Table 1a Material c [Gew.-%] d [nm] ITO 100 90 Metallkomplex 100 3* F1 100 120 ABH113: NUBD370 97:3 20 F3: LiQ 50:50 36 Al 100 100 Die Ergebnisse sind in Tabelle 1b angegeben Table 1b *j = 15 mA / cm 2 U* [V] EQE* [%] CIE-y* **j = 30 mA / cm 2 3 nm Li(TFSI) (Referenz) 5,28 6,6 0,090 3 nm E4 5,16 5,6 0,093 3 nm E9 5,45 5,6 0,098

[0161] It can be concluded that methide complexes as a pure HIL represent an alternative to LiTFSI.

[0162] 2) Using a methide coordination complex as a p-dopant in a hole injection layer included in a blue OLED

[0163] Table 2a describes the model device schematically. Table 2a Material c [Gew.-%] d [nm] ITO 100 90 F1: p-Dotand 92: 8 (mol%) 10 F1 100 120 ABH113: NUBD370 97: 3 20 F3: LiQ 50: 50 36 Al 100 100

[0164] The results are presented in Table 2b. Table 2b *j = 15 mA / cm 2 U* [V] EQE* [%] CIE-y* U(50 h)-U(1h) ** [V] **j = 30 mA / cm 2 Li(TFSI) (Referenz) 8,06 7,1 0,095 0,6 E1 6,50 6,1 0,092 E4 5,03 5,7 0,095 0,37 E9 5,22 5,8 0,097 >3 E23 5,13 5,4 0,096 0,12

[0165] Regarding the operating voltage of the model devices, it was shown that methides were significantly better p-dopants than LiTFSI.

[0166] 3) Using a methide coordination complex as a p-dopant in a hole injection layer included in a blue OLED

[0167] Table 3a describes the model device schematically. Table 3a Material c [Gew.- %] d [nm] ITO 100 90 F1: p-Dotand 92:8 (mol%) 10 F1 100 115 F4 100 5 H09: BD200 97:3 20 F5 100 5 F6: ND2 70:30 31 Yb 100 2 Al 100 100

[0168] The results are shown in Table 3b Table 3b *j = 15 mA / cm 2 U* [V] EQE* [%] CIE-y* U(50 h)-U(1h) ** [V] **j = 30 mA / cm 2 Li(TFSI) (Referenz) 4,59 5,6 0,097 0,49 E4 3,79 9,6 0,100 0,47 E23 3,87 9,5 0,095 0,15

[0169] 4) Using a methide coordination complex as a p-dopant in a solution-processed hole-injection layer incorporated in a blue OLED

[0170] Table 4a describes the model device schematically. Table 4a Material c [Gew.-%] d [nm] ITO 100 90 F2: p-Dotand 92:8 (mol%) 45 F1 100 85 ABH113: NUBD370 97:3 20 F7: LiQ 50:50 36 Al 100 100

[0171] The results are presented in Table 4b. Table 4b *j = 15 mA / cm 2 U* [V] EQE* [%] CIE-y* U(50 h)-U(1h) ** [V] **j = 30 mA / cm 2 Li(TFSI) (Referenz) 4,0 6,2 0,092 0,8 E2 3,9 6,2 0,091 0,3

[0172] The features disclosed in the foregoing description and the dependent claims may, separately or in combination, be subject to realization of the aspects of the disclosure made in the independent claims in different forms thereof.

[0173] Key symbols and abbreviations used in the application: CV cyclic voltammetry DSC Differential Scanning Calorimetry EBL electron-blocking layer EIL electron injection layer EML emitting layer eq. equivalent ETL electron transport layer ETM electron transport matrix Fc Ferrocen FC + Ferricenium HBL hole-blocking layer HIL hole injection layer HOMO highest occupied molecular orbital HPLC high performance liquid chromatography HTL hole transport layer p-HTL p-doped hole transport layer HTM hole transport matrix ITO Indium Tin Oxide LUMO lowest unoccupied molecular orbital mol% mol percent NMR nuclear magnetic resonance OLED organic light-emitting diode OPV organic photovoltaics PTFE Polytetrafluoroethylene QE quantum efficiency R fRetardation factor in TLC RGB red-green-blue TCO transparent conductive oxide TFT thin-film transistor T g Glass transition temperature TLC thin layer chromatography VTE thermal vacuum evaporation wt% weight percent

Claims

[1] An electronic device comprising: a hole injection layer and / or a hole transport layer and / or a hole generating layer, wherein at least one of the hole injection layer, the hole transport layer and the hole generating layer comprises a coordination complex comprising at least one electropositive atom M and at least one anionic methide ligand L represented by the following formula (I): wherein A 1 , A 2 and A 3 each independently selected from the group consisting of (i) partially or fully halogenated C4 to C 30 -tertiary aliphatic or alicyclic hydrocarbyl, (ii) C6 to C 30 -Aryl, (iii) C2 to C 30 -Heteroaryl, (iv) C1 to C 30 - Sulfonyl, and M is selected from the group consisting of a) Li, Na, K, Rb, Cs, each in the oxidation state (I), and b) Be, Mg, Ca, Sr, Ba, Mn, Fe, Co, Ni, Zn, Cd, Sn, Pb, each in the oxidation state (II), where A 1 , A 2 and A 3 are substituted with fluorine, and where in A 1 , A 2 and A 3 the number ratio of fluorine : hydrogen is ≥ 1. [2] The electronic device of claim 1, wherein M is selected from a) Li, Na, K, Rb, Cs, each in the oxidation state (I), and b) Mg, Ca, Sr, Ba, Mn, Fe, Co, Ni, Zn, each in the oxidation state (II). [3] Electronic device according to one of the preceding claims, wherein at least one of A 1 , A 2 and A 3 from C1 to C 30 -sulfonyl is selected. [4] Electronic device according to one of the preceding claims, wherein at least one of A 1 , A 2 and A 3 from C6 to C 30 -aryl and C2-to C 30 -Heteroaryl is selected. [5] An electronic device according to any one of the preceding claims, selected from an organic electroluminescent device, an organic transistor and an organic photovoltaic device. [6] A display device comprising at least two electroluminescent devices according to claim 6. [7] A method of manufacturing the electronic device according to any one of claims 1 to 6 or the display device according to claim 6, the method comprising the steps of (1) evaporating the coordination complex as defined in any one of claims 1 to 4, and (2) Deposition of vapor of the coordination complex on a solid support. [8] A semiconducting material comprising a hole transport matrix material and a p-dopant, wherein the p-dopant is the coordination complex as defined in any one of claims 1 to 4. [9] Coordination complex comprising at least one electropositive atom M and at least one anionic methide ligand L represented by the following formula (I): where A 1 and A 2 each independently from C1 to C 30 - perfluorinated sulfonyl, A 3 from C6 to C 30 - perfluorinated sulfonyl, M is selected from the group consisting of Be, Sr, Ba, Mn, Fe, Co, Ni, Cd, Sn, Pb, each in the oxidation state (II); or which is represented by one of the following formulas

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