Organic electronic devices, organic semiconductor materials and borane compounds

Abstract

The present invention relates to an organic electronic device, an organic semiconductor material and a borane compound. More specifically, the present invention relates to an organic electronic device or an organic semiconductor material comprising a borane compound and a corresponding borane compound, wherein the borane compound comprises at least one boron atom in oxidation state (III) and at least one anionic ligand, wherein the anionic ligand has the formula (Ia) or (Ib), wherein the symbols have the meanings given in the specification. #imgabs0#

Description

Technical Field

[0001] The present invention relates to an organic electronic device, an organic semiconductor material and a borane compound. More specifically, the present invention relates to an organic electronic device or an organic semiconductor material comprising a borane compound and the corresponding borane compound, wherein the borane compound comprises at least one boron atom in oxidation state (III) and at least one anionic ligand according to the present invention. Background Art

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

[0003] When voltage is applied to the anode and cathode, holes injected from the anode electrode move to the EML via the HTL, and electrons injected from the cathode electrode move to the EML via the ETL. Holes and electrons recombine in the EML to generate excitons. When the excitons drop from the excited state to the ground state, light is emitted. The injection and flow of holes and electrons should be balanced so that the OLED having the above structure has excellent efficiency.

[0004] WO 2017 / 029370 A1 discloses metal amides and their use as hole injection layers for organic light-emitting diodes.

[0005] Angewandte Chemie, International Edition 2011, 50, 2098-2101 discloses an air-sensitive vacuum distillable thick liquid compound, which consists of C 10 H 14 BF6NO4S2, the structure is

[0006]

[0007] and assign Chemical Abstracts Service number 1283232-76-7.

[0008] WO 2017 / 029366 A1 discloses a hole injection layer for an organic light-emitting diode, comprising a triarylamine compound doped with a charge-neutral metal amide compound, the hole injection layer having a thickness of 20 to 1,000 nm.

[0009] However, there is still a need to improve the performance of organic electronic devices and / or organic semiconductor materials, in particular the performance of optoelectronic devices comprising organic charge transport materials, such as organic light emitting diodes (OLEDs) or organic photovoltaic (OPV) devices, and the performance of complex devices comprising such optoelectronic devices, such as OLED displays.

[0010] Therefore, the object of the present invention is to provide an organic electronic device and / or organic semiconductor material that overcomes the shortcomings of the prior art, in particular to provide an organic electronic device / organic semiconductor material comprising a hole transport material, a hole injection material, a hole generating material or two or more thereof to improve the performance of the corresponding device, in particular to improve its initial voltage, efficiency or voltage stability. Summary of the invention

[0011] The above objects are achieved by an organic electronic device, comprising a borane compound, the borane compound comprising at least one boron atom in oxidation state (III) and at least one anionic ligand, the anionic ligand having formula (Ia) or (Ib):

[0012]

[0013] Wherein in the formulae (Ia) and (Ib),

[0014] A 1 To A 6 Independently selected from CO, SO2 or POX 1 ;

[0015] X 1 independently selected from halide, nitrile, halogenated or perhalogenated C1 to C 20 Alkyl, halogenated or perhalogenated, C6 to C 20 aryl, and halogenated or perhalogenated heteroaryl having 5 to 20 ring atoms; and

[0016] R 1 To R 6 independently selected from substituted or unsubstituted C1 to C 20 Alkyl, substituted or unsubstituted C1 to C 20 Heteroalkyl, substituted or unsubstituted C6 to C 20 Aryl, and substituted or unsubstituted C5 to C 20 Heteroaryl, where R 1 and R 2 Can be connected to each other to form a ring.

[0017] The group A contained in the anionic ligand having the formula (Ia) or (Ib) 1 To A 6 It is an electron withdrawing group.

[0018] According to the invention, the group R contained in the anionic ligand of formula Ia 1 and R 2 can be connected to each other to form a ring. This means that the group R 1 and R 2 can be linked to each other via covalent bonds, in particular via single covalent bonds. In this case, the two moieties R 1 and R 2 The connection between them is realized in such a way that R 1 A hydrogen atom and R 2 One of the hydrogen atoms in each of the molecules is replaced by a covalent bond.

[0019] The present inventors have surprisingly found that organic electronic devices comprising the inventive borane compounds as defined above show improved electronic properties, in particular improved initial voltage, quantum efficiency and voltage stability.

[0020] The boron atom may be directly bonded to at least one nitrogen atom contained in the anionic ligand via a covalent bond. In this regard, the nitrogen atom directly bonded to the boron atom may be one of the N atoms explicitly shown in the above formulas (Ia) and (Ib) (each having a negative charge in the above formulas), i.e., if the part R 1 To R 6 or X 1 If the nitrogen atom directly bonded to the boron atom is selected as an N-containing heteroalkyl or N-containing heteroaryl group, then the nitrogen atom directly bonded to the boron atom may not be one of the nitrogen atoms that may be contained in these moieties. In this way, the performance of the organic electronic device can be further improved, in particular, further improvement can be achieved with respect to its initial voltage, quantum efficiency and / or voltage stability.

[0021] In the organic electronic device, it may be provided that the structural part X 1 , R 1 , R 2 , R 3 , R 4 , R 5 and R 6 At least 50%, or at least 66%, or at least 75%, or at least 80%, or at least 90%, or at least 100% of the total number of hydrogen atoms contained in at least one part of the organic electronic device are replaced by substituents, wherein the substituents are independently selected from F, Cl, Br, I and CN. In this way, the performance of the organic electronic device can be further improved, in particular, further improvement can be achieved with respect to its initial voltage, quantum efficiency and / or voltage stability.

[0022] In the embodiment outlined above, in which the structural portion R 1 , R 2 , R3 , R 4 , R 5 and R 6 In the case of at least one part of an alkyl group, a specific amount (expressed as a percentage) of hydrogen atoms contained therein is replaced by a substituent, reference is made to the case in which the corresponding part was originally unsubstituted. For example, if 50% of the total number of hydrogen atoms of the alkyl group is replaced by a substituent, reference is made to the unsubstituted alkyl group. In other words, the above embodiments refer to specific cases of substituted parts in which the degree of substitution is at a specific level. In addition, it should be understood that the degree of substitution in the above embodiments refers to the replacement of hydrogen atoms in a single part.

[0023] In the organic electronic device, it can also be provided that at least 50%, or at least 66%, or at least 75%, or at least 80%, or at least 90%, or at least 100% of the total number of hydrogen atoms contained in all structural parts X1, R1, R2, R3, R4, R5 and R6 are replaced by substituents independently selected from F, Cl, Br, I and CN. In this way, the performance of the organic electronic device can be further improved, in particular, further improvement can be achieved with respect to its initial voltage, quantum efficiency and / or voltage stability.

[0024] Furthermore, in this embodiment, the generalized case (hydrogen is replaced by a substituent) is of course referred to the case where the individual moieties are initially unsubstituted alkyl / aryl. This embodiment differs from the above-described embodiments in that reference is made to all moieties X counted together. 1 , R 1 , R 2 , R 3 , R 4 , R 5 and R 6 The total number of hydrogen atoms contained in .

[0025] It is to be understood that the term "electrical properties" refers to the injection and / or transport of electrons in the semiconductor materials and layers comprised in the device as defined herein.

[0026] Regarding the organic electronic device, it can be provided that the organic electronic device comprises a first electrode, a second electrode and an organic semiconductor layer, wherein the organic semiconductor layer is arranged between the first electrode and the second electrode, and the organic semiconductor layer contains a borane compound. In this way, the performance of the organic electronic device can be further improved, in particular, further improvement can be achieved with respect to its initial voltage, quantum efficiency and / or voltage stability.

[0027] Furthermore, it can be provided with respect to the organic electronic device that the organic semiconductor layer is a hole injection layer, a hole transport layer or a hole generation layer. In this way, the performance of the organic electronic device can be further improved, in particular with respect to its initial voltage, quantum efficiency and / or voltage stability.

[0028] In this respect, it can be provided that the organic electronic device comprises two or more of the above-mentioned layers (hole injection layer, hole transport layer and hole generation layer), wherein it can be provided that more than one or all of these layers comprise the boron compound.

[0029] It may also be provided with regard to the organic electronic device that the organic electronic device is an organic electroluminescent device, an organic transistor, an organic diode or an organic photovoltaic device.

[0030] Furthermore, it can be provided that the organic electroluminescent component is an organic light-emitting diode.

[0031] The organic electronic device of the present invention is an organic electronic device comprising at least one organic semiconductor layer (usually multiple organic semiconductor layers). These layers can be prepared, for example, by evaporating a compound and depositing it on a substrate (or a previous layer) to form a layer. According to the present invention, at least one layer of the device can be a hole injection layer, a hole transport layer or a hole generation layer, and contains a borane compound as defined herein. In this regard, it can be provided that, in addition to another material, the borane compound is contained in the layer, for example, in the case where the borane compound is a dopant, the dopant is contained in the layer together with a suitable matrix compound. Similarly, it can be provided that each layer is composed of a borane compound, i.e., the layer does not contain any other ingredients (except impurities that cannot be avoided by conventional technical means). In the case of a layer composed of a borane compound, each layer can be a hole injection layer.

[0032] If the borane compound is an electrical dopant, the electrical dopant, which may be embedded in the charge transporting matrix compound, may improve the conductivity of the matrix material and / or the injection of charges therein. The matrix material in such a layer is the main material.

[0033] It is to be understood that the term "electrical dopant" as used herein refers to a compound that improves the electrical properties of a semiconductor material and / or layer. As a result, the electrical conductivity, operating voltage, voltage rise over time, efficiency and or lifetime of a device including the doped semiconductor material and / or layer may be improved. The electrical dopant may be non-luminescent.

[0034] In the organic electronic device, at least one layer comprising the borane compound may be solid.

[0035] In organic electronic devices, the layer comprising the borane compound may be amorphous. In this regard, a bulk material having a glass transition temperature above room temperature as measured by standard procedures should form an amorphous layer if the layer is provided by the same procedure as the bulk material (e.g. vacuum deposition or by evaporation of a solution of the material in a specific solvent). The standard procedure is described in the experimental section.

[0036] The layer comprising the borane compound may be non-emissive.

[0037] This object is further achieved by an organic semiconductor material comprising a borane compound comprising at least one boron atom in oxidation state (III) and at least one anionic ligand, said anionic ligand having the formula (Ia) or (Ib),

[0038]

[0039] Wherein in the formulae (Ia) and (Ib),

[0040] A 1 To A 6 Independently selected from CO, SO2 or POX 1 ;

[0041] X 1 independently selected from halide, nitrile, halogenated or perhalogenated C1 to C 20 Alkyl, halogenated or perhalogenated, C6 to C 20 aryl, and halogenated or perhalogenated heteroaryl having 5 to 20 ring atoms; and

[0042] R 1 To R 6 independently selected from substituted or unsubstituted C1 to C 20 Alkyl, substituted or unsubstituted C1 to C 20 Heteroalkyl, substituted or unsubstituted C6 to C 20 Aryl, and substituted or unsubstituted C5 to C 20 Heteroaryl, where R 1 and R 2 Can be connected to each other to form a ring.

[0043] In this respect, the embodiments described above with respect to the boron compound contained in an organic electronic device also apply to the case of an organic semiconductor material, as does the technical effect achieved in this way.

[0044] The present inventors surprisingly found that the organic semiconductor material as defined above, when used in an organic electronic device (particularly when used in its hole injection layer, hole transport layer or hole generation layer), helps to improve its initial voltage, quantum efficiency and voltage stability.

[0045] With regard to the organic semiconductor material, it may be provided that it also (in addition to the borane compound) comprises an organic matrix compound.

[0046] The organic semiconductor material may be a hole transport material and the organic matrix compound may be an organic hole transport matrix compound.

[0047] In this respect, it may be provided that the organic hole-transporting matrix compound comprises a conjugated system of at least 6, or at least 10, or at least 14 delocalized electrons.

[0048] In this respect it may further be provided that the organic hole transporting matrix compound is selected from organic compounds comprising at least one amine nitrogen substituted by a group independently selected from aryl and heteroaryl. Non-limiting examples of suitable hole transporting matrix materials are mentioned below.

[0049] It is to be understood that in this context the term "semiconductor" relates to materials and / or devices having an electronic conductivity mechanism. The current in a semiconductor can be explained by the flow of mobile electrons. This is significantly different from electronic devices that utilize ionic conductivity. Such devices (not according to the present invention), such as galvanic cells, contain an electrolyte with mobile ions, and the current therein is accompanied by a flow of ions through the electrolyte.

[0050] Furthermore, the object is achieved by borane compounds of the formula (II),

[0051]

[0052] Where Q 1 and Q 2 independently selected from unsubstituted C1 to C 30 Hydrocarbyl, where Q 1 and Q 2 may be optionally linked to each other to form a ring; and

[0053] Z is an anionic ligand having the formula (Ia) or (Ib),

[0054]

[0055] Wherein in the formulae (Ia) and (Ib),

[0056] A 1 To A 6 Independently selected from CO, SO2 or POX 1 ;

[0057] X 1 independently selected from halide, nitrile, halogenated or perhalogenated C1 to C 20 Alkyl, halogenated or perhalogenated, C6 to C20 Aryl, and halogenated or perhalogenated heteroaryl having 5 to 20 ring atoms;

[0058] R 1 To R 6 independently selected from substituted or unsubstituted C1 to C 20 Alkyl, substituted or unsubstituted C1 to C 20 Heteroalkyl, substituted or unsubstituted C6 to C 20 Aryl, and substituted or unsubstituted C5 to C 20 Heteroaryl, where R 1 and R 2 can be connected to each other to form a ring;

[0059] and

[0060] Excluded are compounds having the formula,

[0061]

[0062] wherein Z is a bis(trifluoromethylsulfonyl)imide anion ligand.

[0063] The present inventors surprisingly found that the borane compound as defined above, when used in an organic electronic device or an organic semiconductor material, in particular in a hole injection layer, a hole transport layer or a hole generation layer, is suitable for improving the initial voltage, quantum efficiency and / or voltage stability of the corresponding device.

[0064] Regarding the borane compound of the present invention, it can be provided that Q 1 and Q 2 Independently selected from C1 to C 30 Alkyl and C1 to C 30 Cycloalkyl.

[0065] Regarding the borane compound of the present invention, it can also be provided that A 1 , A 2 , A 3 , A 4 , A 5 and A 6 Independently selected from SO2 and POX1, or all A 1 , A 2 , A 3 , A 4 , A 5 and A 6 They are all SO2.

[0066] Regarding the borane compound of the present invention, it can also be provided that X 1 , R 1 , R 2 , R3 , R 4 , R 5 and R 6 Each independently selected from halogenated C1 to C 30 Hydrocarbyl, or fully halogenated C1 to C 30 A hydrocarbon group, or a fluorinated C1 to C 30 A hydrocarbon group, or a group selected from perfluorinated C1 to C 30 Hydrocarbon.

[0067] In this regard, it may also be provided that, in the borane compound of the present invention, the moiety X 1 , R 1 , R 2 , R 3 , R 4 , R 5 and R 6 At least 50%, or at least 66%, or at least 75%, or at least 80%, or at least 90%, or at least 100% of the total number of hydrogen atoms contained in at least one portion of the is replaced by substituents, wherein the substituents are independently selected from F, Cl, Br, I and CN.

[0068] Furthermore, it can be provided that, in the compounds of the present invention, all moieties X 1 , R 1 , R 2 , R 3 , R 4 , R 5 and R 6 At least 50%, or at least 66%, or at least 75%, or at least 80%, or at least 90%, or at least 100% of the total number of hydrogen atoms contained in are replaced by substituents independently selected from F, Cl, Br, I and CN.

[0069] It can be provided that the borane compound of the present invention is one or more of the following compounds: compounds E1-E2 of formula (IIa),

[0070]

[0071] Compound E3 having the formula

[0072]

[0073] or one or more of compounds E4-E6 of formula (IIa),

[0074]

[0075] Wherein Z is selected from the structure Z 1 -Z 6 Anionic ligand

[0076]

[0077]

[0078] Using the exemplary compounds, the performance of organic electronic devices can be further improved, in particular, further improvements can be achieved with respect to their initial voltage, efficiency and / or voltage lifespan.

[0079] The object is also achieved by a method for preparing an organic electronic device as defined herein, comprising the following steps:

[0080] (1) dissolving a borane compound comprising at least one boron atom in oxidation state (III) and at least one anionic ligand having the formula (Ia) or (Ib) in a suitable solvent

[0081]

[0082] Wherein in the formulae (Ia) and (Ib),

[0083] A 1 To A 6 Independently selected from CO, SO2 or POX 1 ;

[0084] X 1 independently selected from halide, nitrile, halogenated or perhalogenated C1 to C 20 Alkyl, halogenated or perhalogenated, C6 to C 20 aryl, and halogenated or perhalogenated heteroaryl having 5 to 20 ring atoms; and

[0085] R 1 To R 6 independently selected from substituted or unsubstituted C1 to C 20 Alkyl, substituted or unsubstituted C1 to C 20 Heteroalkyl, substituted or unsubstituted C6 to C 20 Aryl, and substituted or unsubstituted C5 to C 20 Heteroaryl, where R 1 and R 2 can be connected to each other to form a ring; and

[0086] (2) Depositing the borane compound from the solution onto a solid support.

[0087] This object is further achieved by using a borane compound comprising at least one boron atom in oxidation state (III) and at least one anionic ligand having the formula (Ia) or (Ib),

[0088]

[0089] Wherein in the formulae (Ia) and (Ib),

[0090] A 1 To A 6 Independently selected from CO, SO2 or POX 1 ;

[0091] X 1 independently selected from halide, nitrile, halogenated or perhalogenated C1 to C 20 Alkyl, halogenated or perhalogenated, C6 to C 20 aryl, and halogenated or perhalogenated heteroaryl having 5 to 20 ring atoms; and

[0092] R 1 To R 6 independently selected from substituted or unsubstituted C1 to C 20 Alkyl, substituted or unsubstituted C1 to C 20 Heteroalkyl, substituted or unsubstituted C6 to C 20 Aryl, and substituted or unsubstituted C5 to C 20 Heteroaryl, where R 1 and R 2 The borane compounds can be linked to each other to form a ring, and are used for preparing organic electronic devices.

[0093] Other layers

[0094] According to the present invention, in addition to the layers mentioned above, the organic electronic device may further include other layers. Exemplary embodiments of the various layers are described below:

[0095] Base

[0096] The substrate can be any substrate commonly used to manufacture organic electronic devices such as organic light emitting diodes. If light is to be emitted through the substrate, the substrate should be a transparent or translucent material, such as a glass substrate or a transparent plastic substrate. If light is to be emitted through the top surface, the substrate can be a transparent material as well as a non-transparent material, such as a glass substrate, a plastic substrate, a metal substrate or a silicon substrate.

[0097] Anode electrode

[0098] The first electrode or the second electrode can be an anode electrode. The anode electrode can be formed by depositing or sputtering a material for forming the anode electrode. The material for forming the anode electrode can be a high work function material to facilitate hole injection. The anode material can also be selected from a low work function material (i.e., 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 a metal, typically silver (Ag), gold (Au) or a metal alloy.

[0099] Hole injection layer

[0100] According to the present invention, the hole injection layer may include a borane compound as described in great detail above. The hole injection layer (HIL) may be formed on the anode electrode by vacuum deposition, spin coating, printing, casting, slot die coating, Langmuir-Blodgett (LB) deposition, etc. 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, in general, the conditions for vacuum deposition may include a deposition temperature of 100° C. to 500° C., 10 -8 Up to 10 -3 Torr (1 Torr equals 133.322 Pa) pressure, and a deposition rate of 0.1 to 10 nm / s.

[0101] When the HIL is formed using spin coating or printing, the coating conditions may vary according to the compound used to form the HIL and the desired structure and thermal properties of the HIL. For example, the coating conditions may 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. The heat treatment is performed after coating to remove the solvent.

[0102] The HIL can be formed of any compound commonly used to form a HIL, especially when the organic electronic device includes another layer containing a borane compound. Examples of compounds that can be used to form the HIL include phthalocyanine compounds 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).

[0103] In this case, the HIL may be a pure p-type dopant layer, or may be selected from a hole transport host compound doped with a p-type dopant. Typical examples of known redox-doped hole transport materials are: copper phthalocyanine (CuPc) with a HOMO level of about -5.2 eV, which is doped with tetrafluoro-tetracyanoquinodimethane (F4TCNQ) with a LUMO level of about -5.2 eV; zinc phthalocyanine (ZnPc) doped with F4TCNQ (HOMO = -5.2 eV); α-NPD (N,N'-bis(naphthalene-1-yl)-N,N'-bis(phenyl)-benzidine) doped with F4TCNQ; α-NPD (PD1) doped with 2,2'-(perfluoronaphthalene-2,6-diylidene)dimalononitrile; α-NPD (PD2) doped with 2,2',2"-(cyclopropane-1,2,3-triylidene)tris(2-(p-cyanotetrafluorophenyl)acetonitrile). The dopant concentration can be selected from 1 wt% to 20 wt%, more preferably 3 wt% to 10 wt%.

[0104] The thickness of the HIL may be within a range of about 1 nm to about 100 nm, for example, about 1 nm to about 25 nm. When the thickness of the HIL is within this range, the HIL may have excellent hole injection characteristics without a significant loss in driving voltage.

[0105] Hole transport layer

[0106] According to the present invention, the hole transport layer may comprise a borane compound as described in detail above.

[0107] The hole transport layer (HTL) can be formed on the HIL by vacuum deposition, spin coating, slot die coating, printing, casting, Langmuir-Blodgett (LB) deposition, etc. When the HTL is formed by vacuum deposition or spin coating, the conditions of deposition and coating may be similar to those used to form the HIL. However, the conditions of vacuum or solution deposition may vary depending on the compound used to form the HTL.

[0108] In the case where the HTL does not contain the borane compound according to the present invention but the borane compound is contained in another layer, the HTL may be formed of any compound commonly used to form the HTL. Compounds that can be suitably used are disclosed in, for example, Yasuhiko Shirota and Hiroshi Kageyama, Chem. Rev. 2007, 107, 953-1010 and are incorporated by reference. Examples of compounds 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(naphthalene-1-yl)-N,N'-diphenylbenzidine (α-NPD); and triphenylamine-based compounds such as 4,4',4" tris(N-carbazolyl)triphenylamine (TCTA). Among these compounds, TCTA can transport holes and inhibit the diffusion of excitons into the EML.

[0109] 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. The preferred thickness of the HTL may be 170 nm to 200 nm.

[0110] When the thickness of the HTL is within this range, the HTL may have excellent hole transport characteristics without a significant loss in driving voltage.

[0111] Electron blocking layer

[0112] The function of the electron blocking layer (EBL) is to prevent electrons from being transferred from the light-emitting layer to the hole transport layer, thereby confining the electrons in the light-emitting layer. Therefore, the efficiency, operating voltage and / or life are improved. Typically, the electron blocking layer comprises a triarylamine compound. The triarylamine compound may have a LUMO energy level that is closer to the vacuum energy level than the LUMO energy level of the hole transport layer. Compared with the HOMO energy level of the hole transport layer, the electron blocking layer may have a HOMO energy level that is further away from the vacuum energy level. The thickness of the electron blocking layer can be selected between 2nm and 20nm.

[0113] The electron blocking layer may comprise a compound of formula Z as described below (Z).

[0114]

[0115] In formula Z, CY1 and CY2 are the same or different from each other and each independently represents a benzene ring or a naphthalene ring, Ar1 to Ar3 are the same or different from each other and each independently selected from 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 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, and L is a substituted or unsubstituted arylene group having 6 to 30 carbon atoms.

[0116] If the electron blocking layer has a high triplet energy level, it may also be described as a triplet controlling layer.

[0117] If a phosphorescent green or blue emitting layer is used, the function of the triplet control layer is to reduce the quenching of the triplet state. Thus, a higher luminous efficiency from the phosphorescent emitting layer can be achieved. The triplet control layer is selected from triarylamine compounds, whose triplet energy level is higher than the triplet energy level of the phosphorescent emitter in the adjacent emitting layer. Suitable compounds for triplet control layers, in particular triarylamine compounds, are described in EP 2 722 908 A1.

[0118] Emission layer (EML)

[0119] The EML can be formed on the HTL by vacuum deposition, spin coating, slot die coating, printing, casting, LB deposition, etc. When the EML is formed using vacuum deposition or spin coating, the conditions of deposition and coating may be similar to those used to form the HIL. However, the conditions of deposition and coating may vary depending on the compound used to form the EML.

[0120] The light-emitting layer (EML) may be formed of a composition of a host and a light-emitting dopant. Examples of the host are Alq3, 4,4'-N,N'-dicarbazole-biphenyl (CBP), poly(N-vinylcarbazole) (PVK), 9,10-di(naphthalene-2-yl)anthracene (ADN), 4,4',4"-tri(carbazole-9-yl)-triphenylamine (TCTA), 1,3,5-tri(N-phenylbenzimidazol-2-yl)benzene (TPBI), 3-tert-butyl-9,10-di-2-naphthylanthracene (TBADN), distyrylarene (DSA), bis(2-(2-hydroxyphenyl)benzothiazole)zinc (Zn(BTZ)2), G3 below, compound 1 below, and compound 2 below.

[0121]

[0122] The emitter dopant may be a phosphorescent or fluorescent emitter. Phosphorescent emitters and emitters emitting via a thermally activated delayed fluorescence (TADF) mechanism may be preferred due to their higher efficiency. The emitter may be a small molecule or a polymer.

[0123] Examples of red emitter dopants are PtOEP, Ir(piq)3 and Btp2lr(acac), but are not limited thereto. These compounds are phosphorescent emitters, but fluorescent red emitter dopants may also be used.

[0124]

[0125] Examples of phosphorescent green emitter dopants are Ir(ppy)3 (ppy = phenylpyridine), Ir(ppy)2(acac), Ir(mpyp)3, as shown below. Compound 3 is an example of a fluorescent green emitter and its structure is shown below.

[0126]

[0127] Examples of phosphorescent blue emitter dopants are F2Irpic, (F2ppy)2Ir(tmd) and Ir(dfppz)3, terfluorene, the structure of which is shown below. 4,4'-bis(4-diphenylaminophenylvinyl)biphenyl (DPAVBi), 2,5,8,11-tetra-tert-butylperylene (TBPe) and compound 4 below are examples of fluorescent blue emitter dopants.

[0128]

[0129] The amount of the luminophore dopant may be in the range of about 0.01 to about 50 parts by weight based on 100 parts by weight of the host. Alternatively, the luminescent layer may be composed of a luminescent polymer. The EML may have a thickness of about 10 nm to about 100 nm, for example, about 20 nm to about 60 nm. When the thickness of the EML is within this range, the EML may have excellent luminescence without a significant loss in driving voltage.

[0130] Hole Blocking Layer (HBL)

[0131] A hole blocking layer (HBL) may be formed on the EML to prevent holes from diffusing into the ETL by using vacuum deposition, spin coating, slot die coating, printing, casting, LB deposition, etc. When the EML includes a phosphorescent dopant, the HBL may also have a triplet exciton blocking function.

[0132] When the HBL is formed using vacuum deposition or spin coating, the conditions for deposition and coating may be similar to those for forming the HIL. However, the conditions for deposition and coating may vary depending on the compound used to form the HBL. Any compound commonly used to form the HBL may be used. Examples of compounds used to form the HBL include Oxadiazole derivatives, triazole derivatives and phenanthroline derivatives.

[0133] The HBL may have a thickness in the range of about 5 nm to about 100 nm, for example, about 10 nm to about 30 nm. When the thickness of the HBL is within this range, the HBL may have excellent hole blocking properties without a significant loss in driving voltage.

[0134] Electron Transport Layer (ETL)

[0135] The OLED according to the invention may contain an electron transport layer (ETL).

[0136] According to various embodiments, the OLED may include an electron transport layer or an electron transport layer stack including at least a first electron transport sublayer and at least a second electron transport sublayer.

[0137] By properly adjusting the energy level of a specific layer of the ETL, the injection and transport of electrons can be controlled, and holes can be effectively blocked. Therefore, the OLED can have a long lifespan.

[0138] The electron transport layer of the organic electronic device may include an organic electron transport matrix (ETM) material. In addition, the electron transport layer may include one or more n-type dopants. There is no particular limitation on the compounds suitable for ETM. In 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 of delocalized electrons may be contained in an aromatic or heteroaromatic structure, as disclosed in, for example, EP 1 970 371 A1 or WO 2013 / 079217 A1.

[0139] In one embodiment, the electron transport layer may be electrically doped with an n-type electrical dopant. In another embodiment, the electron transport layer may include a second electron transport sublayer disposed closer to the cathode than the first electron transport sublayer, and only the second electron transport sublayer may include an n-type electrical dopant.

[0140] The n-type electrical dopant may be selected from electropositive elemental metals, and / or metal salts and metal complexes of electropositive metals, in particular elemental forms, salts and / or complexes of metals selected from alkali metals, alkaline earth metals and rare earth metals.

[0141] Electron injection layer (EIL)

[0142] An optional EIL that can facilitate electron injection from the cathode can be formed on the ETL, preferably directly on the electron transport layer. Examples of materials for forming the EIL include 8-hydroxyquinoline lithium (LiQ), LiF, NaCl, CsF, Li2O, BaO, Ca, Ba, Yb, Mg known in the art. The deposition and coating conditions for forming the EIL are similar to those for forming the HIL, but the deposition and coating conditions may vary depending on the material used to form the EIL.

[0143] 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 within this range, the EIL may have satisfactory electron injection characteristics without significantly reducing driving voltage.

[0144] Cathode electrode

[0145] The cathode electrode is formed on the EIL (if present). The cathode electrode may be formed of a metal, an alloy, a conductive compound, or a mixture thereof. The cathode electrode may have a low work function. For example, the cathode electrode may be formed of lithium (Li), magnesium (Mg), aluminum (Al), aluminum (Al)-lithium (Li), calcium (Ca), barium (Ba), ytterbium (Yb), magnesium (Mg)-indium (In), magnesium (Mg)-silver (Ag), etc. Alternatively, the cathode electrode may be formed of a transparent conductive oxide such as ITO or IZO.

[0146] 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 translucent even if formed of a metal or a metal alloy.

[0147] It is to be understood that the cathode electrode is not part of the electron injection layer or the electron transport layer.

[0148] Charge generation layer / hole generation layer

[0149] The charge generation layer (CGL) may consist of a double layer. In the case where the charge generation layer is a p-type charge generation layer (hole generation layer), it may comprise a borane compound as defined herein.

[0150] Typically, the charge generation layer is a pn junction connecting an n-type charge generation layer (electron generation layer) and a hole generation layer. The n-side of the pn junction generates electrons and injects them into the layer adjacent to the anode direction. Similarly, the p-side of the pn junction generates holes and injects them into the layer adjacent to the cathode direction.

[0151] The charge generation layer is used in a tandem device, for example, in a tandem OLED comprising two or more light-emitting layers between two electrodes. In a tandem OLED comprising two light-emitting layers, the n-type charge generation layer provides electrons to a first light-emitting layer arranged near the anode, and the hole generation layer provides holes to a second light-emitting layer arranged between the first light-emitting layer and the cathode.

[0152] According to the present invention, it can be provided that the organic electronic device includes a hole injection layer and a hole generation layer. If another layer other than the hole generation layer contains a borane compound as defined herein, the hole generation layer does not necessarily contain a borane compound as defined herein. In this case, the hole generation layer may be composed of an organic matrix material doped with a p-type dopant. The matrix material suitable for the hole generation layer may be a material conventionally used as a hole injection and / or hole transport matrix material. In addition, conventional materials may be used for the p-type dopant for the hole generation layer. For example, the p-type dopant may be one selected from the following: tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ), tetracyanoquinodimethane derivatives, axialene derivatives, iodine, FeCl3, FeF3 and SbCl5. In addition, the host can be one selected from the following: N,N'-di(naphthalene-1-yl)-N,N-diphenyl-benzidine (NPB), N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1-biphenyl-4,4'-diamine (TPD) and N,N',N'-tetranaphthyl-benzidine (TNB).

[0153] In one embodiment, the hole generating layer comprises a borane compound as defined in detail above.

[0154] The n-type charge generation layer can be a pure n-type dopant layer, such as a positive metal layer, or can be composed of an organic matrix material doped with an n-type dopant. In one embodiment, the n-type dopant can be an alkali metal, an alkali metal compound, an alkaline earth metal or an alkaline earth metal compound. In another embodiment, the metal can be one selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, La, Ce, Sm, Eu, Tb, Dy and Yb. More specifically, the n-type dopant can be one selected from Cs, K, Rb, Mg, Na, Ca, Sr, Eu and Yb. The matrix material suitable for the electron generation layer can be a material conventionally used as a matrix material for electron injection or electron transport layer. The matrix material can be, for example, one selected from triazine compounds, hydroxyquinoline derivatives such as tris (8-hydroxyquinoline) aluminum, indole derivatives and silole derivatives.

[0155] In one embodiment, the n-type charge generation layer may include a compound of the following Chemical Formula X.

[0156]

[0157] Among them A 1 To A 6 Each of them can be hydrogen, a halogen atom, a nitrile (-CN), a nitro group (-NO2), a sulfonyl group (-SO2R), a sulfoxide (-SOR), a sulfonamide (-SO2NR), a sulfonate (-SO3R), a trifluoromethyl group (-CF3), an ester (-COOR), an amide (-CONHR or -CONRR'), a substituted or unsubstituted straight chain or branched C1-C12 alkoxy group, a substituted or unsubstituted straight chain or branched C1-C12 alkyl group, a substituted or unsubstituted straight chain or branched C2-C12 alkenyl group, a substituted or unsubstituted aromatic or non-aromatic heterocycle, a substituted or unsubstituted aryl group, a substituted or unsubstituted monoarylamine or diarylamine, a substituted or unsubstituted arylalkylamine, etc. Here, each of the above R and R' may be a substituted or unsubstituted C1-C60 alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted 5- to 7-membered heterocyclic ring.

[0158] An example of such an n-type charge generation layer may be a layer containing CNHAT,

[0159]

[0160] The hole generation layer is disposed on top of the n-type charge generation layer.

[0161] Organic Light Emitting Diode (OLED)

[0162] According to one aspect of the present invention, an organic light emitting diode (OLED) is provided, which includes: a substrate; an anode electrode formed on the substrate; a hole injection layer, a hole transport layer, a light emitting layer and a cathode electrode.

[0163] According to another aspect of the present invention, an OLED is provided, which includes: a substrate; an anode electrode formed on the substrate; a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer and a cathode electrode.

[0164] According to another aspect of the present invention, an OLED is provided, which includes: a substrate; an anode electrode formed on the substrate; a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer and a cathode electrode.

[0165] According to another aspect of the present invention, an OLED is provided, which includes: a substrate; an anode electrode formed on the substrate; a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer and a cathode electrode.

[0166] According to various embodiments of the present invention, an OLED may be provided, which includes a layer disposed between the above-mentioned layers, on a substrate, or on a top electrode.

[0167] According to one aspect, an OLED may include the following layer structure: a substrate, which is arranged adjacent to an anode electrode, the anode electrode is arranged adjacent to a first hole injection layer, the first hole injection layer is arranged adjacent to a first hole transport layer, the first hole transport layer is arranged adjacent to a first electron blocking layer, the first electron blocking layer is arranged adjacent to a first light-emitting layer, the first light-emitting layer is arranged adjacent to a first electron transport layer, the first electron transport layer is arranged adjacent to an n-type charge generation layer, the n-type charge generation layer is arranged adjacent to a hole generation layer, the hole generation layer is arranged adjacent to a second hole transport layer, the second hole transport layer is arranged adjacent to a second electron blocking layer, the second electron blocking layer is arranged adjacent to a second light-emitting layer, and an optional electron transport layer and / or an optional injection layer are arranged between the second light-emitting layer and the cathode electrode.

[0168] For example, according to Figure 2 The OLED can be formed by the following process, wherein an anode (120), a hole injection layer (130), a hole transport layer (140), an electron blocking layer (145), a light emitting layer (150), a hole blocking layer (155), an electron transport layer (160), an electron injection layer (180) and a cathode electrode (190) are subsequently formed on a substrate (110).

[0169] Details and definitions of the invention

[0170] The organic electronic device of the invention comprises at least one (semiconductor) layer, which may comprise a charge transport matrix compound and a borane compound. The borane compound may be embedded in a matrix material, i.e. the matrix material is the main material in such a layer. Likewise, it may be provided that in the semiconductor layer, the matrix material and the dopant are separated from one another, the matrix material being included in the first sublayer and the dopant being included in the second sublayer, or in a preferred embodiment, the first sublayer and the second sublayer are composed of the matrix material and the dopant, respectively. Likewise, it may be provided that the layer consists of a borane compound.

[0171] The borane compound may diffuse into adjacent layers after deposition, and in particular the borane compound may diffuse into the layer on which it is deposited.

[0172] The organic electronic device described herein may be an organic electronic device based on a semiconductor layer. In particular, the hole injection layer, the hole transport layer and the hole generation layer are semiconductor layers.

[0173] The term "hydrocarbyl group" as used herein is understood to include any organic group comprising carbon atoms, in particular organic groups such as alkyl, aryl, heteroaryl, heteroalkyl, in particular such groups as conventional substituents in organic electronics.

[0174] As used herein, the term "alkyl" shall include straight chain as well as branched and cyclic alkyl groups. For example, a C3 alkyl group may be selected from n-propyl and isopropyl. Similarly, a C4 alkyl group includes n-butyl, sec-butyl and tert-butyl. Similarly, a C6 alkyl group includes n-hexyl and cyclohexyl.

[0175] C n The subscript number n in <EMI ID=11.1> relates to the total number of carbon atoms in the corresponding alkyl, arylene, heteroarylene or aryl group.

[0176] As used herein, the term "aryl" shall include phenyl (C6 aryl), fused aromatic compounds such as naphthalene, anthracene, phenanthrene, tetracene, etc. Also included are biphenyl and oligomeric or polymeric phenyl groups such as terphenyl, etc. Also included are any other aromatic hydrocarbon substituents such as fluorenyl, etc. Arylene or heteroarylene refers to a group connected to two additional moieties.

[0177] The term "heteroaryl" as used herein refers to an aryl group wherein at least one carbon atom is replaced by a heteroatom preferably selected from N, O, S, B or Si.

[0178] 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 meanings of the terms "fluorinated" and "perfluorinated" should be understood similarly.

[0179] C n The subscript number n in 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, Azoles, thiazoles, etc.

[0180] For the purposes of the present invention, the expression "between" with respect to a layer being between two other layers does not exclude the presence of other layers that may be arranged between the one layer and one of the two other layers. For the purposes of the present invention, the expression "in direct contact" with respect to two layers being in direct contact with each other means that no other layer is arranged between the two layers. A layer deposited on top of another layer is considered to be in direct contact with this layer.

[0181] In the context of this specification, the term "substantially non-luminescent" or "non-luminescent" means that the contribution of a compound or layer to the visible emission spectrum from a device is less than 10%, preferably less than 5%, relative to the visible emission spectrum. The visible emission spectrum is the emission spectrum with a wavelength of about ≥380 nm to about ≤780 nm.

[0182] Preferably, the organic semiconductor layer comprising at least one electrical dopant is substantially non-luminescent or non-luminescent.

[0183] With regard to the electronic device of the present invention, the compounds mentioned in the experimental part may be most preferred.

[0184] The electronic device of the present invention may be an organic electroluminescent device (OLED), an organic photovoltaic device (OPV) or an organic field effect transistor (OFET).

[0185] According to another aspect, the organic electroluminescent device according to the invention may comprise more than one light-emitting layer, preferably two or three light-emitting layers. OLEDs comprising more than one light-emitting layer are also described as tandem OLEDs or stacked OLEDs.

[0186] Organic electroluminescent devices (OLEDs) can be bottom or top emitting devices.

[0187] Another aspect relates to a device comprising at least one organic electroluminescent device (OLED).A device comprising an organic light emitting diode is, for example, a display or a lighting panel.

[0188] In the present invention, these definitions shall apply to the following defined terms, unless a different definition is given in the claims or elsewhere in this specification.

[0189] In the context of this specification, the term "different" or "different" in relation to a host material means that the structural formula of the host material is different.

[0190] The energy levels of the highest occupied molecular orbital (also known as HOMO) and the lowest unoccupied molecular orbital (also known as LUMO) are measured in electron volts (eV).

[0191] The terms "OLED" and "organic light emitting diode" are used concurrently and have the same meaning. The term "organic electroluminescent device" as used herein may include an organic light emitting diode as well as an organic light emitting transistor (OLET).

[0192] As used herein, "weight percent," "wt%" and variations thereof refer to a composition, component, substance or agent in the form of the weight of the component, substance or agent of the corresponding electron transport layer divided by the total weight of its corresponding electron transport layer and multiplied by 100. It is understood that the total weight percentage of all components, substances and agents of the corresponding electron transport layer and electron injection layer is selected such that it does not exceed 100 weight percent.

[0193] As used herein, "volume percent," "volume %" and variations thereof refer to a composition, component, substance, or agent in the form of the volume of the component, substance, or agent of the corresponding electron transport layer divided by the total volume of its corresponding electron transport layer and multiplied by 100. It is understood that the total volume percentage of all components, substances, and agents of the cathode layer is selected such that it does not exceed 100 volume %.

[0194] It is assumed herein that all numerical values ​​are modified by the term "about", whether or not explicitly indicated. As used herein, the term "about" refers to the possible changes in the quantity. Whether or not modified by the term "about", the claims include equivalents of the quantity.

[0195] It should be noted that, as used in this specification and the claims, the singular forms "a," "an," and "the" include plural referents unless the content clearly dictates otherwise.

[0196] The terms "does not contain", "does not contain", "does not include" do not exclude impurities. For the purposes of the present invention, impurities have no technical effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0197] These and / or other aspects and advantages of the present invention will become apparent and more readily understood from the following description of exemplary embodiments taken in conjunction with the accompanying drawings, in which:

[0198] Figure 1 is a schematic cross-sectional view of an organic light emitting diode (OLED) according to an exemplary embodiment of the present invention;

[0199] Figure 2 is a schematic cross-sectional view of an OLED according to an exemplary embodiment of the present invention;

[0200] Figure 3 is a schematic cross-sectional view of a tandem OLED including a charge generation layer according to an exemplary embodiment of the present invention. DETAILED DESCRIPTION

[0201] Reference will now be made in detail to exemplary embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to like elements throughout. Exemplary embodiments are described below in order to explain aspects of the present invention by referring to the drawings.

[0202] Here, 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.

[0203] Figure 11 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 substrate 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 directly formed on the EML 150. On the electron transport layer (ETL) 160, an electron injection layer (EIL) 180 is provided. The cathode 190 is directly provided on the electron injection layer (EIL) 180.

[0204] Optionally, a stack of electron transport layers (ETL) may be used instead of the single electron transport layer 160 .

[0205] Figure 2 is a schematic cross-sectional view of an OLED 100 according to another exemplary embodiment of the present invention. Figure 2 and Figure 1 The difference is Figure 2 The OLED 100 includes an electron blocking layer (EBL) 145 and a hole blocking layer (HBL) 155 .

[0206] See also Figure 2 , the OLED 100 includes a substrate 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.

[0207] Figure 3 is a schematic cross-sectional view of a tandem OLED 200 according to another exemplary embodiment of the present invention. Figure 3 and Figure 2 The difference is Figure 3 The OLED 100 further includes a charge generating layer and a second light emitting layer.

[0208] See also Figure 3, the OLED 200 includes a substrate 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 light emitting layer (EML) 150, a first hole blocking layer (HBL) 155, 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 light emitting 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.

[0209] Although in Figure 1 , Figure 2 and Figure 3 Although not shown in the drawings, a sealing layer may be further formed on the cathode electrode 190 to seal the OLEDs 100 and 200. In addition, various other modifications may be applied thereto.

[0210] Hereinafter, one or more exemplary embodiments of the present invention will be described in detail with reference to the following examples. However, these examples are not intended to limit the purpose and scope of one or more exemplary embodiments of the present invention.

[0211] Experimental Section

[0212] The formula of the supporting material mentioned below is as follows:

[0213] F1 is

[0214]

[0215] (Poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(4,4'-(N-(4-sec-butylphenyl)diphenylamine)], available from Solaris Chem Inc)

[0216] F2 is

[0217]

[0218] N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluoren-2-amine, CAS 1242056-42-3;

[0219] F3 is

[0220]

[0221] 8-(4-(4,6-di(naphthalen-2-yl)-1,3,5-triazin-2-yl)phenyl)quinoline, CAS 1312928-44-1;

[0222] ABH-113 is the emitter host and NUBD-370 and DB-200 are blue fluorescent emitter dopants, all available from SFC, Korea.

[0223] ITO is indium tin oxide.

[0224] Preparation of Exemplary Compounds

[0225] General Synthetic Procedure A

[0226] A suspension of 0.5 equivalents of 9-borahertabicyclo[3.3.1]nonane dimer (1.0 equivalents of monomer) and 1.0 equivalents of the corresponding imide in anhydrous toluene was carefully heated at 90° C. for 1 hour under a dry N2 atmosphere. Strong gas release was observed while heating, and a clear solution was formed. The resulting solution was vacuum distilled. Compounds E2 and E1 were isolated as fractions boiling at 100-120° C. (1.5 torr). Solid compounds E4, E5 and E6 were separated by filtration and washed with anhydrous hexane.

[0227] Synthesis of compound E3

[0228] A suspension of 0.5 equivalents of dimesityl borane dimer (1.0 equivalents of monomer) and 1.0 equivalents of the corresponding imide in anhydrous toluene was carefully heated at 90°C for 1 hour under a dry N2 atmosphere. Strong gas release was observed while heating, and a clear solution was formed. The resulting solution was vacuum distilled. The product was washed with anhydrous hexane.

[0229] E1

[0230]

[0231] Yield 54%, white solid;

[0232] 1 H NMR (600MHz, CDCl3): δ=1.13-1.15(m,1H),1.37-1.41(m,2H),1.46-1.50(m,1H),1.81-1.94(m,10H);

[0233] 19 F NMR (377MHz,CDCl3):δ=-126.12(m,4F),-120.93(m,4F),-106.17(br s,4F),-81.07(t,J=9.6Hz,6F); due to multiple 19 F,19 F coupling and further separation;

[0234] 11 B NMR (192MHz, CDCl3): δ = 59.2 (s).

[0235] E2

[0236]

[0237] Yield 51%, yellow viscous liquid;

[0238] 1 H NMR (600MHz, C6D6): δ = 1.12-1.15 (m, 2H), 1.61-1.70 (m, 12H);

[0239] 11 B NMR (192MHz, C6D6): δ = 71 (s); 59 (s)

[0240] E3

[0241]

[0242] Yield 57%, light yellow solid;

[0243] 1 H NMR (600MHz, C6D6): δ = 2.14 (s, 6H, 2xMe), 2.27 (s, 12H, 4xMe), 6.74 (s, 4H, H Ar );

[0244] 11 B NMR (192MHz, C6D6): δ = 57.8 (s).

[0245] E4

[0246]

[0247] Yield 55%, yellow solid;

[0248] 1 H NMR (600MHz, C6D6): δ = 1.31-1.36 (m, 3H), 1.87-1.96 (m, 10H), 2.86 (s, 1H);

[0249] 11 B NMR (192 MHz, C6D6): δ=66.0 (s); optional 58.3 (s).

[0250] E5

[0251]

[0252] Yield 60%, light yellow solid;

[0253] 1 H NMR(600MHz,C6D6):1.30-1.32(m,2H),1.83-1.93(m,6H),1.98-2.05(m,4H),2.94(s,2H),6.68-6.72(m,2H,H Ar ),7.11(d, 3 J=6.5Hz,1H,H Ar ),7.44(d, 3 J=6.3Hz,1H,H Ar ); 11 B NMR (192 MHz, C6D6): δ = 62.8 (s); optional 58.0 (s)

[0254] E6

[0255]

[0256] Yield 58%, light yellow solid;

[0257] 1 H NMR (600MHz, C6D6): δ=1.20-1.25(m,2H),1.68-1.76(m,2H),1.80-1.83(m,4H),1.98-2.04(m,4H),2.69(s,2H),6.41-6.42(m,2H,H Ar ),6.95-6.97(m,2H,H Ar ); 11 B NMR (192MHz, C6D6): δ = 60.7 (s).

[0258] The depicted structures are schematic and are 11 The presence of multiple signals observed in the B NMR spectrum demonstrates that the coordination mode of the anionic ligand has changed.

[0259] Device experiments

[0260] Standard Procedure

[0261] Voltage stability

[0262] OLEDs are driven by constant current circuits. These circuits can provide a constant current within a given voltage range. The wider the voltage range, the wider the power loss of such devices. Therefore, it is necessary to minimize the change in the driving voltage when driving.

[0263] The driving voltage of OLED is temperature-dependent. Therefore, the voltage stability needs to be judged under thermal equilibrium. Thermal equilibrium is reached after one hour of driving.

[0264] The voltage stability was measured by taking the driving voltage difference after driving at a constant current density for 50 hours and 1 hour. Here, 30 mA / cm 2 The measurements were performed at room temperature.

[0265] dU[V]=U(50h,30mA / cm 2 )–U(1h,30mA / cm 2 )

[0266] Example

[0267] Blue fluorescent OLED including a hole injection layer p-doped with an acyliminoborane compound

[0268] Table 1a schematically describes the model device.

[0269] Table 1a

[0270]

[0271] #Based on molar amount of metal atoms

[0272] The results are given in Table 2b

[0273] Table 1b

[0274]

[0275] With regard to initial voltage and EQE, E1 and E2 perform at least as well or even better than the comparative material LiTFSI. In addition, for E2, better performance in terms of voltage stability is observed.

[0276] The features disclosed in the preceding description and in the dependent claims may, both alone and in any combination thereof, be material for realizing the aspects of the disclosure set out in the independent claims in their various forms.

[0277] Key symbols and abbreviations used throughout this application:

[0278] CV Cyclic Voltammetry

[0279] DSC Differential Scanning Calorimetry

[0280] EBL electron blocking layer

[0281] EIL Electron Injection Layer

[0282] EML Emissive Layer

[0283] eq. equivalent

[0284] ETL electron transport layer

[0285] ETM Electron Transport Matrix

[0286] Fc Ferrocene

[0287] Fc + Ferrocene ion

[0288] HBL Hole Blocking Layer

[0289] HIL Hole Injection Layer

[0290] HOMO Highest occupied molecular orbital

[0291] HPLC High Performance Liquid Chromatography

[0292] HTL Hole Transport Layer

[0293] p-HTL p-type doped hole transport layer

[0294] HTM Hole Transport Matrix

[0295] ITO Indium Tin Oxide

[0296] LUMO lowest unoccupied molecular orbital

[0297] mol% molar percentage

[0298] NMR Nuclear Magnetic Resonance

[0299] OLED Organic Light Emitting Diode

[0300] OPV Organic Photovoltaic Devices

[0301] PTFE Polytetrafluoroethylene

[0302] QE Quantum Efficiency

[0303] R f Delay Factor in TLC

[0304] RGB Red-Green-Blue

[0305] TCO Transparent Conductive Oxide

[0306] TFT Thin Film Transistor

[0307] T g Glass transition temperature

[0308] TLC Thin layer chromatography

[0309] VTE Vacuum Thermal Evaporation

[0310] Weight % Weight percentage

Claims

1. An organic electronic device comprising a first electrode, a second electrode and an organic semiconductor layer, wherein the organic semiconductor layer is arranged between the first electrode and the second electrode, and the organic semiconductor layer comprises a borane compound, the borane compound comprising at least one boron atom in oxidation state (III) and at least one anionic ligand, the anionic ligand having formula (Ia) or (Ib), Wherein in formula (Ia) and (Ib), A 1 To A 6 Independently selected from CO, SO 2 or POX 1 ; X 1 independently selected from halide, nitrile, halogenated or perhalogenated C 1 To C 20 Alkyl, halogenated or perhalogenated C 6 To C 20 aryl, and halogenated or perhalogenated heteroaryl having 5 to 20 ring atoms; and R 1 To R 6 Independently selected from substituted or unsubstituted C 1 To C 20 Alkyl, substituted or unsubstituted C 1 To C 20 Heteroalkyl, substituted or unsubstituted C 6 To C 20 Aryl, and substituted or unsubstituted C 5 To C 20 Heteroaryl, where R 1 and R 2 Can be connected to each other to form a ring. 2 . The organic electronic device according to claim 1 , wherein the boron atom is directly bonded to at least one nitrogen atom included in the anionic ligand via a covalent bond.

3. The organic electronic device according to claim 1 or 2, wherein the structural part X 1 , R 1 , R 2 , R 3 , R 4 , R 5 and R 6 At least 50% of the total number of hydrogen atoms contained in at least one portion of is replaced by substituents, wherein the substituents are independently selected from F, Cl, Br, I and CN.

4. The organic electronic device according to claim 1 or 2, wherein all the structural parts X 1 , R 1 , R 2 , R 3 , R 4 , R 5 and R 6 At least 50% of the total number of hydrogen atoms contained in are replaced together with substituents independently selected from F, Cl, Br, I and CN. 5 . The organic electronic device according to claim 1 , wherein the organic semiconductor layer is a hole injection layer, a hole transport layer or a hole generation layer. 6 . The organic electronic device according to claim 1 , wherein the organic electronic device is an organic electroluminescent device, an organic transistor, an organic diode or an organic photovoltaic device. The organic electronic device according to claim 6 , wherein the organic electroluminescent device is an organic light emitting diode.

8. An organic semiconductor material comprising the borane compound defined in any one of claims 1 to 4.

9. A borane compound having formula (II), Where Q 1 and Q 2 independently selected from unsubstituted C 1 To C 30 Hydrocarbyl, where Q 1 and Q 2 may be optionally linked to each other to form a ring; and Z is an anionic ligand having the formula (Ia) or (Ib), Wherein in the formulae (Ia) and (Ib), A 1 To A 6 Independently selected from CO, SO 2 or POX 1 ; X 1 independently selected from halide, nitrile, halogenated or perhalogenated C 1 To C 20 Alkyl, halogenated or perhalogenated C 6 To C 20 Aryl, and halogenated or perhalogenated heteroaryl having 5 to 20 ring atoms; R 1 To R 6 Independently selected from substituted or unsubstituted C 1 To C 20 Alkyl, substituted or unsubstituted C 1 To C 20 Heteroalkyl, substituted or unsubstituted C 6 To C 20 Aryl, and substituted or unsubstituted C 5 To C 20 Heteroaryl, where R 1 and R 2 can be connected to each other to form a ring; and Excluded are compounds having the formula, wherein Z is a bis(trifluoromethylsulfonyl)imide anion ligand.

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