Organic electronic device, display device comprising the same, a compound and its use, and a method for producing the compound

Abstract

An organic electronic device (100) comprising an anode layer (120), a cathode layer (190), an emission layer (150) and a semiconductor layer, comprising a first compound, wherein the first compound has the formula (I), wherein - R 1 up to R4 are independently selected from the group consisting of F, halogen-substituted C1 to C 12 -Alkyl and H, wherein at least two of R 1 to R 4 are selected from F and halogen-substituted C1 to C 12 -Alkyl; - R 1' to R 4' are independently selected from the group consisting of F, halogen-substituted C1- to C 12 -Alkyl and H, wherein at least two of R 1' to R 4' are selected from F and halogen-substituted C1 to C 12 -Alkyl; - Ar 1 and Ar 2 are independently selected from the group consisting of substituted C6-bis C18 -Aryl, unsubstituted C2- to C 17 -Heteroaryl and substituted C2-bisC 17 -Heteroaryl; - the substituted C6 to C 18 -Aryl is substituted with at least one substituent independently selected from the group consisting of halogen, CN and halogen-substituted C1- to C 12 -Alkyl; and - the substituted C2- to C 17 -Heteroaryl is substituted with at least one substituent independently selected from the group consisting of halogen, CN and halogen-substituted C1- to C 12 -Alkyl.

Description

[0001] The present invention relates to an organic electronic device and a display device comprising the same. The invention further relates to a compound and its uses, as well as a method for producing the compound.

[0002] Organic semiconductor devices, such as organic light-emitting diodes (OLEDs), which are self-emitting devices, exhibit a wide viewing angle, excellent contrast, fast response, high brightness, excellent operating voltage characteristics, and color rendering. A typical OLED comprises an anode, a high-hole transport layer (HTL), an emissive layer (EML), an electron transport layer (ETL), and a cathode, stacked sequentially on a substrate. The HTL, EML, and ETL are thin films composed of organic compounds.

[0003] When a voltage is applied to the anode and cathode, holes injected from the anode move through the high-temperature transfer (HTL) to the electron microlayer (EML), and electrons injected from the cathode move through the electron microlayer (ETL) to the EML. The holes and electrons recombine in the EML to generate excitons. When the excitons transition from an excited state to a ground state, light is emitted. The injection and flux of holes and electrons must be balanced so that an OLED with the structure described above exhibits excellent efficiency and / or a long lifetime.

[0004] The performance of an organic light-emitting diode can be influenced by properties of the organic semiconductor layer and can be influenced by properties of an organic material within the organic semiconductor layer.

[0005] In particular, the development of an organic semiconductor layer capable of increasing electron mobility while simultaneously increasing electrochemical stability is required so that the organic semiconductor device, such as an organic light-emitting diode, can be applied to a large flat panel display.

[0006] Furthermore, the development of an organic semiconductor layer capable of extended lifetime at higher current density and thus higher brightness is required. In particular, the development of an organic semiconductor material or layer capable of lowering the operating voltage is necessary, which is important, for example, for mobile display devices to reduce power consumption and increase battery life.

[0007] US 2003 / 006414 A1 discloses the use of halogenated triarylborane compounds, such as tris(pentafluorophenyl)borane, as p-dopers in organic semiconductor materials. However, these compounds suffer from unsuitably high volatility, hygroscopicity, and hydrolytic instability.

[0008] DE 10 2010 056 519 A1 discloses an organic electronic or optoelectronic component comprising an electrode and a counter electrode as well as a layer system between the electrode and the counter electrode, wherein the layer system contains at least one organic layer and at least one doped layer, wherein the dopant in the doped layer, based on the calculation of the fluoride ion affinity, represents a stronger Lewis acid than antimony pentafluoride (SbF5) or a stronger Lewis base than 1,8-bis(dimethylamino)naphthalene.

[0009] Metz, VM et al., Angew. Chem. Int. Ed., Vol. 39, 2000, No. 7, S 1313-1316 discloses organo-Lewisic acid cocatalysts in the single-site olefin polymerization and in this context a highly acidic perfluorodiboraanthracene.

[0010] Reus C et al. J. Am. Chem. Soc., Vol. 135, 2013, pp. 12892-12907, discloses C-functionalized air- and water-stable 9,10-dihydro-9,10-diboraanthracenes.

[0011] Radke J. et al., Chem. Sci., Vol. 10 , 2019, p. 9017-9027, discloses the selective access to a double boron-doped tetrabenzopentacene or an oxadiborepin from the same precursor.

[0012] US 2020 / 0347081A1 relates to the field of organic electroluminescent materials and, in particular, compounds with thermally activated delayed fluorescence (TADF) properties, which contain an aromatic heterocyclic ring, a display field containing the compound, and a display device. CN 111100152A discloses a material with delayed fluorescence by thermal activation, a synthesis method, and an electroluminescent device.

[0013] Müller P. et al. Z. Naturforsch., Vol. 50 b, 1995, p. 1476-1484 reveals the synthesis and structures of 9,10-Dihydro-9,10-diboraanthracene derivatives.

[0014] It is therefore the object of the present invention to provide compounds and semiconductor materials for the manufacture of organic electronic devices and display devices that overcome the disadvantages of the prior art, in particular to provide p-doping materials for the manufacture of organic electronic devices with good processability, especially p-doping materials that enable organic electronic devices with improved performance. SUMMARY OF THE INVENTION

[0015] The above problem is solved by an organic electronic device comprising an anode layer, a cathode layer, an emission layer and a semiconductor layer, comprising a first compound, wherein the first compound has the formula (I) wherein - R 1 to R 4 are independently selected from the group consisting of F, halogen-substituted C1- to C12 -Alkyl and H, wherein at least two of R 1 to R 4 are selected from F and halogen-substituted C1 to C 12 -Alkyl; - R 1' to R 4' are independently selected from the group consisting of F, halogen-substituted C1- to C 12 -Alkyl and H, wherein at least two of R 1' to R 4' are selected from F and halogen-substituted C1 to C 12 -Alkyl; - Ar 1 and Ar 2 are independently selected from the group consisting of substituted C6bis C 18 -Aryl, unsubstituted C2- to C 17 -Heteroaryl and substituted C2- to C 17 -Heteroaryl; - the substituted C6 to C 18 -Aryl is substituted with at least one substituent independently selected from the group consisting of halogen, CN and halogen-substituted C1- to C 12 -Alkyl; and - the substituted C2- to C 17 -Heteroaryl is substituted with at least one substituent independently selected from the group consisting of halogen, CN and halogen-substituted C1- to C 12 -Alkyl.

[0016] This problem is further solved by a display device comprising at least one, preferably at least two, organic electronic devices according to the present invention, wherein the organic electronic device is an organic light-emitting diode.

[0017] This task is further accomplished by a connection with formula (Ib) where - R 1 to R 4 are independently selected from the group consisting of F, halogen-substituted C1- to C 12 -Alkyl and H, wherein at least two of R 1 to R 4 are selected from F and halogen-substituted C1 to C 12 -Alkyl; - R 1' to R 4'are independently selected from the group consisting of F, halogen-substituted C1- to C 12 -Alkyl and H, wherein at least two of R 1' to R 4' are selected from F and halogen-substituted C1 to C 12 -Alkyl; - Ar 1 and Ar 2 are independently selected from the group consisting of substituted C6bis C 18 -Aryl, unsubstituted C2- to C 17 -Heteroaryl and substituted C2- to C 17 -Heteroaryl; - the substituted C6 to C 18 -Aryl is substituted with at least one substituent independently selected from the group consisting of halogen, CN and halogen-substituted C1- to C 12 -Alkyl, wherein at least one of the substituents of the substituted C6- to C 18 -Aryls is selected from the group consisting of CN and halogen-substituted C1- to C 12 -Alkyl; and - the substituted C2- to C 17-Heteroaryl is substituted with at least one substituent independently selected from the group consisting of halogen, CN and halogen-substituted C1- to C 12 -Alkyl.

[0018] This problem is further solved by using the compound according to the invention with formula (I) or the compound according to the invention with formula (Ib) as a p-doping agent in an organic semiconductor material or in a hole injection layer.

[0019] This problem is further solved by a method for producing a compound of formula (I), wherein the method comprises a step of Converting a compound of formula (II) with a compound of formula (III) and with a compound of formula (IV) M 1 -Ar 1 (III) M 2 -Ar 2 (IV) or with a combination of the formula (V) Ar 1 -M 3 -Ar 2 (V) to obtain the connection of formula (Ib) wherein - R 1 to R 4 are independently selected from the group consisting of F, halogen-substituted C1- to C 12 -Alkyl and H, wherein at least two of R 1 to R 4 are selected from F and halogen-substituted C1 to C 12 -Alkyl; - R 1' to R 4' are independently selected from the group consisting of F, halogen-substituted C1- to C 12 -Alkyl and H, wherein at least two of R 1' to R 4' are selected from F and halogen-substituted C1 to C 12 -Alkyl; - Ar 1 and Ar 2 are independently selected from the group consisting of substituted C6bis C 18 -Aryl, unsubstituted C2- to C 17 -Heteroaryl and substituted C2- to C 17 -Heteroaryl; - the substituted C6 to C 18-Aryl is substituted with at least one substituent independently selected from the group consisting of halogen, CN and halogen-substituted C1- to C 12 -Alkyl, wherein at least one of the substituents of the substituted C6- to C 18 -Aryls is selected from the group consisting of CN and halogen-substituted C1- to C 12 -Alkyl; - the substituted C2- to C 17 -Heteroaryl is substituted with at least one substituent independently selected from the group consisting of halogen, CN and halogen-substituted C1- to C 12 -Alkyl; - Hal 1 and Hal 2 are independently selected from halogen; - M 1 and M 2 are independently selected from M'R''', where M' is a metal and R' is independently selected from the group consisting of an electron donor compound and a halogen, where m is an integer from 0 to 2; - M3 independent from M''R'' n is selected where M'' is a metal and R'' is independently a hydrocarbyl group, where n is an integer from 0 to 2.

[0020] Surprisingly, it was found that suitably substituted diboraanthracene compounds can be used as p-dopers in organic semiconductor materials and, unlike borane compounds known in the prior art, such as in US 2003 / 006414 A1, can be deposited by thermal vacuum evaporation processes in a prior art apparatus. Organic electronic device

[0021] According to one aspect, the invention relates to an organic electronic device. The organic electronic device comprises an anode layer, a cathode layer, an emission layer, and a semiconductor layer. Further layers that may be included in the organic electronic device are described below. first connection

[0022] The semiconductor layer includes a first junction. The first junction has the following formula (I)

[0023] In formula (I) R 1 to R 4 independently selected from the group consisting of F, halogen-substituted C1- to C 12 -Alkyl and H, wherein at least two of R 1 to R 4 from F and halogen-substituted C1 to C 12 -Alkyl are selected. R 1 to R 4can be independently selected from the group consisting of F, halogen-substituted C1 to C4 alkyl and H, wherein at least two of R 1 to R 4 Selected are from F and halogen-substituted C1bisC4 alkyl. R 1 to R 4 may be independently selected from the group consisting of F, fully halogen-substituted C1- to C4-alkyl and H, wherein at least two of R 1 to R 4 The selected compounds are F and fully halogen-substituted C1 to C4 alkyl. In this context, "fully substituted" means that each hydrogen atom of the respective alkyl group is replaced by a halogen atom. R 1 to R 4 can be independently selected from the group consisting of F, F-substituted C1 to C4 alkyl and H, wherein at least two of R 1 to R 4 are selected from F and F-substituted C1- to C4-alkyl. R 1 to R 4can be independently selected from the group consisting of F, fully F-substituted C1bisC4 alkyl and H, wherein at least two of R 1 to R 4 are selected from F and fully F-substituted C1- to C4-alkyl. R 1 to R 4 can be independently selected from the group consisting of F, CF3 and H, where at least two of R 1 to R 4 Selected are from F and CF3. R 1 to R 4 can be independently selected from the group consisting of F and H, where at least two of R 1 to R 4 F are.

[0024] In formula (I) R 1' to R 4' independently selected from the group consisting of F, halogen-substituted C1- to C 12 -Alkyl and H, wherein at least two of R 1' to R 4' are selected from F and halogen-substituted C1 to C 12 -Alkyl. R 1' to R 4'can be independently selected from the group consisting of F, halogen-substituted C1 to C4 alkyl and H, wherein at least two of R 1' to R 4' are selected from F and halogen-substituted C1- to C4-alkyl. R 1' to R 4' may be independently selected from the group consisting of F, fully halogen-substituted C1- to C4-alkyl and H, wherein at least two of R 1' to R 4' The selected compounds are F and fully halogen-substituted C1 to C4 alkyl. In this context, "fully substituted" means that each hydrogen atom of the respective alkyl group is replaced by a halogen atom. R 1' to R 4' can be independently selected from the group consisting of F, F-substituted C1 to C4 alkyl and H, wherein at least two of R 1' to R 4' are selected from F and F-substituted C1- to C4-alkyl. R 1' to R 4'can be independently selected from the group consisting of F, fully F-substituted C1- to C4-alkyl and H, wherein at least two of R 1' to R 4' are selected from F and fully F-substituted C1- to C4-alkyl. R 1' to R 4' can be independently selected from the group consisting of F, CF3 and H, where at least two of R 1' to R 4' Selected are from F and CF3. R 1' to R 4' can be independently selected from the group consisting of F and H, where at least two of R 1' to R 4' F are.

[0025] It may be provided that R 1 to R 4 and R 1' to R 4' are independently selected from F, CN or CF3; or - R 1 to R 3 and R 2 ' to R 4' are F, independently selected from F, CN or CF3, and R 4 and R 1'are H; or - R 2 , R 3 , R 2' and R 3' are independently selected from F, CN or CF3, and R 1 ; R 4 , R 1' and R 4' are H.

[0026] It may be provided that R 1 to R 4 and R 1' to R 4' F are; or - R 1 to R 3 and R 2 ' to R 4' are F, and R 4 and R 1' are H; or - R 2 , R 3 , R 2 ' and R 3' are F, and R 1 ; R 4 , R 1' and R 4' are H.

[0027] It may be provided that R 2 , R 3 , R 2 ' and R 3' are independently selected from F, CN or CF3 and R 1 ; R 4 , R 1' and R 4' are H.

[0028] It may be provided that R 2 , R 3 , R 2 ' and R 3' are F; and R 1 ; R 4 , R 1' and R 4' are H.

[0029] Ar 1 and Ar 2 are independently selected from the group consisting of substituted C6 to C 18 -Aryl (such as phenyl, 1,1'-biphenyl-4-yl, naphthyl, anthracenyl, phenanthrenyl), unsubstituted C2- to C 17 -Heteroaryl (such as triazine, diazine, pyrazine, pyrimidine, pyridine, quinazoline or benzoquinazoline) and substituted C2- to C 17 -Heteroaryl (such as triazine, diazine, pyrazine, pyrimidine, pyridine, quinazoline or benzoquinazoline). Ar 1 and Ar 2 can be independently selected from the group consisting of substituted C6 to C 12 -Aryl, unsubstituted C2- to C 11 -Heteroaryl and substituted C2- to C 11 -Heteroaryl. Ar 1 and Ar 2can be independently selected from the group consisting of substituted phenyl, unsubstituted C3- to C5-heteroaryl, and substituted C3- to C5-heteroaryl. Ar 1 and Ar 2 can be independently selected from the group consisting of substituted phenyl, unsubstituted pyridyl and substituted pyridyl.

[0030] Ar 1 and Ar 2 can be independently selected from the group consisting of C6 to C 18 -Aryl, substituted with at least three substituents, unsubstituted C2- to C 17 -Heteroaryl and C2- to C 17 -Heteroaryl, substituted with at least three substituents. Ar 1 and Ar 2 can be independently selected from the group consisting of C6 to C 12 -Aryl, substituted with at least three substituents, unsubstituted C2- to C 11 -Heteroaryl and C2- to C 11 -Heteroaryl, substituted with at least three substituents. Ar1 and Ar 2 can be independently selected from the group consisting of phenyl substituted with at least three substituents, unsubstituted C3- to C5-heteroaryl, and C3- to C5-heteroaryl substituted with at least three substituents. 1 and Ar 2 can be independently selected from the group consisting of phenyl substituted with at least three substituents, unsubstituted pyridyl and pyridyl substituted with at least three substituents.

[0031] Ar 1 and Ar 2 can be independently selected from the group consisting of fully substituted C6 to C 18 -Aryl, unsubstituted C2- to C 17 -Heteroaryl and fully substituted C2- to C 17 -Heteroaryl. Ar 1 and Ar 2 can be independently selected from the group consisting of fully substituted C6 to C 12 -Aryl, unsubstituted C2- to C 11-Heteroaryl and fully substituted C2- to C 11 -Heteroaryl. Ar 1 and Ar 2 can be independently selected from the group consisting of fully substituted phenyl, unsubstituted C3- to C5-heteroaryl, and fully substituted C3- to C5-heteroaryl. Ar 1 and Ar 2 can be independently selected from the group consisting of fully substituted phenyl, unsubstituted pyridyl and fully substituted pyridyl.

[0032] In the event that Ar 1 and / or Ar 2 substituted C6 to C 18 -Aryl is / are (including any of the aforementioned respective restricted embodiments), is / are one or more substituents independently selected from the group consisting of halogen, CN and halogen-substituted C1- to C 12 -Alkyl. In the event that Ar 1 and / or Ar 2 substituted C6 to C 18-Aryl is / are (including any of the aforementioned respective restricted embodiments), is / are one or more substituents independently selected from the group consisting of F, Cl, Br, I, CN, F-substituted C1- to C 12 -Alkyl, Cl-substituted C1- to C 12 -Alkyl, Br-substituted C1- to C 12 -Alkyl and I-substituted C1bis C 12 -Alkyl. In the event that Ar 1 and / or Ar 2 substituted C6 to C 18 -Aryl is / are (including any of the aforementioned respective restricted embodiments), is / are one or more substituents independently selected from the group consisting of F, CN and F-substituted C1- to C 12 -Alkyl.

[0033] In the event that Ar 1 and / or Ar 2 substituted C6 to C 18-Aryl is / are (including any of the aforementioned respective restricted embodiments), the one or more substituents are independently selected from the group consisting of halogen, CN, and halogen-substituted C1- to C4-alkyl. In the event that Ar 1 and / or Ar 2 substituted C6 to C 18 -Aryl is / are (including any of the aforementioned respective restricted embodiments), is / are one or more substituents independently selected from the group consisting of F, Cl, Br, I, CN, F-substituted C1- to C4-alkyl, Cl-substituted C1- to C 12 -Alkyl, Br-substituted C1- to C4-alkyl, and I-substituted C1bis C4-alkyl. In the event that Ar 1 and / or Ar 2 substituted C6 to C 18-Aryl is / are (including any of the aforementioned respective restricted embodiments), is / are one or more substituents independently selected from the group consisting of F, CN and F-substituted C1- to C4-alkyl.

[0034] In the event that Ar 1 and / or Ar 2 substituted C6 to C 18 -Aryl is / are (including any of the aforementioned respective restricted embodiments), the one or more substituents is / are independently selected from the group consisting of halogen, CN, and fully halogen-substituted C1- to C4-alkyl. In the event that Ar 1 and / or Ar 2 substituted C6 to C 18-Aryl is / are (including any of the aforementioned respective restricted embodiments), is / are one or more substituents independently selected from the group consisting of F, Cl, Br, I, CN, fully F-substituted C1- to C4-alkyl, fully Cl-substituted C1- to C 12 -Alkyl, fully Br-substituted C1- to C4-alkyl, and fully I-substituted C1- to C4-alkyl. In the event that Ar 1 and / or Ar 2 substituted C6 to C 18 -Aryl is / are (including any of the aforementioned respective restricted embodiments), the one or more substituents is / are independently selected from the group consisting of F, CN and fully F-substituted C1- to C4-alkyl. In the event that Ar 1 and / or Ar 2 substituted C6 to C 18-Aryl is / are (including any of the aforementioned respective restricted embodiments), is / are one or more substituents independently selected from the group consisting of F, CN and CF3.

[0035] In the event that Ar 1 and / or Ar 2 substituted C6 to C 18 -Aryl is / are, the respective substituted C6- to C 18 -Aryl independent Fully substituted phenyl, wherein the substituents are independently selected from F, CN and CF3, preferably the substituents in the 2, 3, 5 and 6 positions of the phenyl are each F and the substituent in the 4 position of the phenyl is CF3 or CN; or 2,4,6-substituted phenyl, wherein the substituent at the 2-position of the phenyl, the substituent at the 4-position of the phenyl and the substituent at the 6-position of the phenyl are independently selected from the group consisting of F, CN and CF3, preferably CN and CF3.

[0036] It may be provided that - at least one, preferably both, of Ar 1 and Ar 2 independently selected from the group consisting of substituted C6 to C 18 -Aryl; and - the substituted C6 to C 18 -Aryl is substituted with at least one substituent independently selected from the group consisting of halogen, CN and halogen-substituted C1- to C 12 -Alkyl, wherein at least one of the substituents is selected from the group consisting of CN and halogen-substituted C1- to C 12 -Alkyl.

[0037] It may be provided that - at least one, preferably both, of Ar 1 and Ar 2 independently selected from the group consisting of substituted C6 to C 18 -Aryl; and - the substituted C6 to C 18 -Aryl is substituted with at least one substituent which is independently selected from the group consisting of F, CN and CF3, wherein at least one of the substituents is selected from the group consisting of CN and CF3.

[0038] In the event that Ar 1 and / or Ar 2 substituted C2- to C 17 -Heteroaryl is / are (including any of the aforementioned respective restricted embodiments), is / are one or more substituents independently selected from the group consisting of halogen, CN and halogen-substituted C1- to C 12 -Alkyl. In the event that Ar 1 and / or Ar 2 substituted C2- to C 17-Heteroaryl is / are (including any of the aforementioned respective restricted embodiments), is / are one or more substituents independently selected from the group consisting of F, Cl, Br, I, CN, F-substituted C1bis C 12 -Alkyl, Cl-substituted C1- to C 12 -Alkyl, Br-substituted C1- to C 12 -Alkyl and I-substituted C1- to C 12 -Alkyl. In the event that Ar 1 and / or Ar 2 substituted C2- to C 17 -Heteroaryl is / are (including any of the aforementioned respective restricted embodiments), is / are one or more substituents independently selected from the group consisting of F, CN and F-substituted C1- to C 12 -Alkyl.

[0039] In the event that Ar 1 and / or Ar 2 substituted C2- to C 17-Heteroaryl is / are (including any of the aforementioned respective restricted embodiments), is / are one or more substituents independently selected from the group consisting of halogen, CN, and halogen-substituted C1- to C4-alkyl. In the event that Ar 1 and / or Ar 2 substituted C2- to C 17 -Heteroaryl is / are (including any of the aforementioned respective restricted embodiments), is / are one or more substituents independently selected from the group consisting of F, Cl, Br, I, CN, F-substituted C1 to C4 alkyl, Cl-substituted C1 to C 12 -Alkyl, Br-substituted C1- to C4-alkyl, and I-substituted C1- to C4-alkyl. In the event that Ar 1 and / or Ar 2 substituted C2- to C 17-Heteroaryl is / are (including any of the aforementioned respective restricted embodiments), is / are one or more substituents independently selected from the group consisting of F, CN and F-substituted C1- to C4-alkyl.

[0040] In the event that Ar 1 and / or Ar 2 substituted C2- to C 17 -Heteroaryl is / are (including any of the aforementioned respective restricted embodiments), is / are one or more substituents independently selected from the group consisting of halogen, CN, and fully halogen-substituted C1- to C4-alkyl. In the event that Ar 1 and / or Ar 2 substituted C2- to C 17-Heteroaryl is / are (including any of the aforementioned respective restricted embodiments), is / are one or more substituents independently selected from the group consisting of F, Cl, Br, I, CN, fully F-substituted C1- to C4-alkyl, fully Cl-substituted C1- to C 12 -Alkyl, fully Br-substituted C1- to C4-alkyl, and fully I-substituted C1- to C4-alkyl. In the event that Ar 1 and / or Ar 2 substituted C2- to C 17 -Heteroaryl is / are (including any of the aforementioned respective restricted embodiments), is / are one or more substituents independently selected from the group consisting of F, CN and fully F-substituted C1- to C4-alkyl. In the event that Ar 1 and / or Ar 2 substituted C2- to C 17-Heteroaryl is / are (including any of the aforementioned respective restricted embodiments), is / are one or more substituents independently selected from the group consisting of F, CN and CF3. In the event that Ar 1 and / or Ar 2 substituted C2- to C 17 -Heteroaryl is / are (including any of the aforementioned respective restricted embodiments), is / are the one or more substituents F.

[0041] It may be provided that Ar 1 selected from groups of the following structures Ar 1 -1 to Ar 1 -5 where the respective structure is bound to *1 in order to

[0042] It may be provided that Ar 2 selected from groups of the following structures Ar 2 -1 to Ar 2 -5 where the respective structure is bound to *2 in order to

[0043] It may be provided that Ar 1 and Ar2 are selected the same way.

[0044] The first connection can be selected from E1 to E10. Semiconductor layer

[0045] The semiconductor layer can comprise the first compound of formula (I) as the predominant material. The semiconductor layer can consist essentially of the first compound of formula (I). The semiconductor layer can consist of the first compound of formula (I). The fact that the semiconductor layer in this alternative consists of the first compound of formula (I) does not preclude impurities. Impurities have no technical effect with regard to the problem solved by the present invention. Impurities are not intentionally added to the layer during processing.

[0046] The semiconductor layer can be a hole injection layer, especially if the semiconductor layer consists (essentially) of the first compound of formula (I).

[0047] Alternatively, the semiconductor layer can comprise at least one further connection (second connection). The second connection can be a hole transport matrix connection, in particular an organic hole transport matrix connection.

[0048] The semiconductor layer can be a p-type hole transport layer and / or charge generation layer, especially if the semiconductor layer additionally comprises a hole transport matrix compound, in particular an organic hole transport matrix compound.

[0049] The organic hole transport matrix compound can comprise a conjugated system of at least 6 delocalized electrons, alternatively at least 10 delocalized electrons, or alternatively at least 14 delocalized electrons.

[0050] The organic hole transport matrix compound can be selected from organic compounds comprising at least one amine nitrogen substituted with groups independently selected from C6 to C6. 42 -Aryl and C3- to C 42 -Heteroaryl.

[0051] Examples of the second compound that can be used to form the semiconductor layer together with the first compound 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'-diphenylbenzidine (alpha-NPD); and triarylamine derivatives, e.g., triphenylamine-based compounds such as 4,4',4''-tris(N-carbazolyl)triphenylamine (TCTA).

[0052] The semiconductor layer can consist of the first compound of formula (I) or comprise the first compound of formula (I) in an amount of up to 100 wt%, based on the total weight of the semiconductor layer.

[0053] The semiconductor layer may contain the first compound of formula (I) in an amount of less than 50 wt%, based on the total weight of the semiconductor layer. The semiconductor layer may contain the first compound of formula (I) in an amount of less than 40 wt%, based on the total weight of the semiconductor layer. The semiconductor layer may contain the first compound of formula (I) in an amount of less than 30 wt%, based on the total weight of the semiconductor layer. The semiconductor layer may contain the first compound of formula (I) in an amount of less than 20 wt%, based on the total weight of the semiconductor layer. The semiconductor layer may contain the first compound of formula (I) in an amount of less than 15 wt%, based on the total weight of the semiconductor layer. The semiconductor layer may contain the first compound of formula (I) in an amount of less than 10 wt%.-%, based on the total weight of the semiconductor layer. The semiconductor layer may contain the first compound of formula (I) in an amount of less than 5 wt%, based on the total weight of the semiconductor layer. The semiconductor layer may contain the first compound of formula (I) in an amount of less than 3 wt%, based on the total weight of the semiconductor layer.

[0054] The semiconductor layer may contain the first compound of formula (I) in an amount of 0.01 to 50 wt%, based on the total weight of the semiconductor layer. The semiconductor layer may contain the first compound of formula (I) in an amount of 0.05 to 40 wt%, based on the total weight of the semiconductor layer. The semiconductor layer may contain the first compound of formula (I) in an amount of 0.1 to 30 wt%, based on the total weight of the semiconductor layer. The semiconductor layer may contain the first compound of formula (I) in an amount of 0.25 to 20 wt%, based on the total weight of the semiconductor layer. The semiconductor layer may contain the first compound of formula (I) in an amount of 0.5 to 10 wt%, based on the total weight of the semiconductor layer. The semiconductor layer may contain the first compound of formula (I) in an amount of 1 to 5 wt%, based on the total weight of the semiconductor layer.The semiconductor layer may contain the first compound of formula (I) in an amount of 1 to 3 wt.%, such as 2 wt.%, based on the total weight of the semiconductor layer.

[0055] The thickness of the semiconductor layer can be in the range of approximately 5 nm to approximately 250 nm, preferably approximately 10 nm to approximately 200 nm, furthermore approximately 20 nm to approximately 190 nm, furthermore approximately 40 nm to approximately 180 nm, furthermore approximately 60 nm to approximately 170 nm, furthermore approximately 80 nm to approximately 160 nm, furthermore approximately 100 nm to approximately 160 nm, furthermore approximately 120 nm to approximately 140 nm. A preferred thickness of the HTL can be 170 nm to 200 nm. Additional layers

[0056] According to the invention, the organic electronic device can comprise additional layers besides those already mentioned above. Exemplary embodiments of the respective layers are described below: substrate

[0057] The substrate can be any substrate commonly used in the fabrication of organic electronic devices, such as organic light-emitting diodes (OLEDs). If light is to be emitted through the substrate, it should 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 an opaque material, for example, a glass substrate, a plastic substrate, a metal substrate, or a silicon substrate. anode electrode

[0058] Either the first or the second electrode can be an anode electrode. The anode electrode can be formed by depositing or sputtering a material used to create it. The material used to form the anode electrode can be a high-work-value material to facilitate hole injection. The anode material can also be selected from a low-work-value material (i.e., aluminum). The anode electrode can be transparent or reflective. 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.Another alternative material for the anode electrode could be graphene. Hole injection layer

[0059] According to the invention, the hole injection layer can comprise the first compound with formula (I) according to the invention, preferably consisting of it.

[0060] 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) deposition, or similar processes. When the HIL is formed using vacuum deposition, the deposition conditions can vary depending on the compound used to form the HIL and the desired structure and thermal properties of the HIL. However, vacuum deposition conditions generally include a deposition temperature of 100 °C to 500 °C and a pressure of 10 -8 up to 10 -3Torr (1 Torr corresponds to 133.322 Pa) and a deposition rate of 0.1 to 10 nm / s.

[0061] When HIL is formed using rotary coating or printing, coating conditions can vary depending on the compound used to form the HIL, the desired structure, and the thermal properties of the HIL. For example, coating conditions may include a coating speed of approximately 2000 rpm to approximately 5000 rpm and a thermal treatment temperature of approximately 80 °C to approximately 200 °C.

[0062] The HIL can be formed from any compound commonly used to form an HIL, particularly if the organic electronic device comprises another layer comprising the first compound with formula (I) according to the invention. 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).

[0063] In such a case, the HIL can be a pure p-doper layer or can be selected from a hole transport matrix compound doped with a p-doper. Typical examples of known redox-doped hole transport materials are: copper phthalocyanine (CuPc), whose HOMO level is approximately -5.2 eV, doped with tetrafluorotetracyanoquinodimedimethane (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; α-NPD, doped with 2,2'-(perfluoronaphthalene-2,6-diylidene)dimalononitrile (PD1). α-NPD doped with 2,2',2''-(cyclopropane-1,2,3-triylidene)tris(2-(p-cyanotetrafluorophenyl)acetonitrile) (PD2). Dopant concentrations can be selected from 1 to 20 wt%, preferably from 3 wt% to 10 wt%.

[0064] The thickness of the HIL can range from approximately 1 nm to approximately 100 nm, and for example, from approximately 1 nm to approximately 25 nm. If the thickness of the HIL is within this range, the HIL can exhibit excellent hole injection properties without a significant loss in drive voltage. Hole transport layer

[0065] According to the invention, the hole transport layer can comprise the first compound with formula (I) according to the invention.

[0066] 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, or similar processes. If the HTL is formed by vacuum deposition or spin coating, the deposition and coating conditions may be similar to those used for HIL formation. However, the vacuum or solution deposition conditions may vary depending on the compound used to form the HTL.

[0067] If the HTL does not comprise the first compound with formula (I) according to the invention, but the first compound with formula (I) is included in another layer, the HTL can be formed by any compound commonly used to form an HTL. Compounds that can be suitable for use are disclosed, for example, in Yasuhiko Shirota and Hiroshi Kageyama, Chem. Rev. 2007, 107, 953-1010 and included 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'-diphenylbenzidine (alpha-NPD); and triphenylamine-based compounds, such as 4,4',4''-Tris(N-carbazolyl)triphenylamine (TCTA).Among these compounds, TCTA can transport holes and prevent excitons from diffusing out of the EML.

[0068] The thickness of the HTL can be in the range of approximately 5 nm to approximately 250 nm, preferably approximately 10 nm to approximately 200 nm, furthermore approximately 20 nm to approximately 190 nm, furthermore approximately 40 nm to approximately 180 nm, furthermore approximately 60 nm to approximately 170 nm, furthermore approximately 80 nm to approximately 160 nm, furthermore approximately 100 nm to approximately 160 nm, furthermore approximately 120 nm to approximately 140 nm. A preferred thickness of the HTL can be 170 nm to 200 nm.

[0069] If the thickness of the HTL is within this range, the HTL can exhibit excellent hole transport properties without a significant loss in drive voltage. Electron blocking layer

[0070] The function of the electron blocking layer (EBL) is to prevent electrons from being transferred from the emission layer to the hole transport layer, thereby confining electrons to the emission 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 closer to the vacuum level than the LUMO level of the hole transport layer. The electron blocking layer can have a HOMO level further from the vacuum level than the HOMO level of the hole transport layer. The thickness of the electron blocking layer can be selected between 2 and 20 nm.

[0071] The electron blocking layer can comprise a compound of formula Z below (Z).

[0072] In formula Z, CY1 and CY2 are either the same or different from each other and each independently represents a benzene cycle or a naphthalene cycle, Ar 1 to Ar 3 are identical or different from each other and each independently selected from the group consisting of hydrogen; a substituted or unsubstituted aryl group with 6 to 30 carbon atoms; and a substituted or unsubstituted heteroaryl group with 5 to 30 carbon atoms, Ar 4 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 triphenyl group and a substituted or unsubstituted heteroaryl group with 5 to 30 carbon atoms, L is a substituted or unsubstituted arylene group with 6 to 30 carbon atoms.

[0073] If the electron blocking layer has a high triplet level, it can also be described as a triplet control layer.

[0074] The function of the triplet control layer is to reduce triplet quenching when a phosphorescent green or blue emission layer is used. This allows for higher light emission efficiency from the phosphorescent emission layer. The triplet control layer is selected from triarylamine compounds with a triplet level higher than that of the phosphorescent emitter in the adjacent emission layer. Suitable compounds for the triplet control layer, particularly the triarylamine compounds, are described in EP 2 722 908 A1. Emission layer (EML)

[0075] The EML can be formed on the HTL by vacuum deposition, spin coating, slot die coating, printing, casting, LB deposition, or similar processes. When the EML is formed using vacuum deposition or spin coating, the deposition and coating conditions can be similar to those used for HIL formation. However, the deposition and coating conditions may vary depending on the compound used to form the EML.

[0076] The emission layer (EML) can be formed from a combination of a host and an emitter dopant. Examples of the host are Alq3, 4,4'-N,N'-dicarbazolebiphenyl (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-hydroxyphenyl)benzothiazolate)zinc (Zn(BTZ)2), G3 below, compound 1 below, and compound 2 below.

[0077] 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.

[0078] Examples of red emitter dopants include PtOEP, Ir(piq)3, and Btp2lr(acac), but these are not the only examples. These compounds are phosphorescent emitters; however, fluorescent red emitter dopants could also be used.

[0079] 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.

[0080] Examples of phosphorescent blue emitter dopants are F₂Irpic, (F₂ppy)₂Ir(tmd), and Ir(dfppz)₃, tert-fluorines; their structures are shown below. 4,4'-Bis(4-diphenylstyryl)biphenyl (DPAVBi), 2,5,8,11-tetra-tert-butylperylene (TBPe), and compound 4 below are examples of fluorescent blue emitter dopants.

[0081] The amount of emitter dopant can range from approximately 0.01 to approximately 50 parts by weight, based on 100 parts by weight of the host. Alternatively, the emission layer can consist of a light-emitting polymer. The EML can have a thickness of approximately 10 nm to approximately 100 nm, for example, from approximately 20 nm to approximately 60 nm. If the thickness of the EML is within this range, the EML can exhibit excellent light emission without a significant loss in the drive voltage. Hole-blocking layer (HBL)

[0082] A hole-blocking layer (HBL) can be formed on the EML using vacuum deposition, rotational coating, slot die coating, printing, casting, LB deposition, or similar processes to prevent the diffusion of holes into the ETL. If the EML includes a phosphorescent dopant, the HBL can also exhibit triplet exciton blocking functionality.

[0083] When HBL is formed using vacuum deposition or spin coating, the deposition and coating conditions can be similar to those for HIL formation. 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 employed. Examples of compounds used to form HBLs include oxadiazole derivatives, triazole derivatives, and phenanthroline derivatives.

[0084] The HBL can have a thickness in the range of approximately 5 nm to approximately 100 nm, for example, from approximately 10 nm to approximately 30 nm. If the thickness of the HBL is within this range, the HBL can exhibit excellent hole-blocking properties without a significant loss in the drive voltage. Electron transport layer (ETL)

[0085] The OLED according to the present invention can contain an electron transport layer (ETL).

[0086] According to various embodiments, the OLED can comprise an electron transport layer or an electron transport layer stack comprising at least one first electron transport sublayer and at least one second electron transport sublayer.

[0087] By appropriately adjusting the energy levels of specific ETL layers, the injection and transport of electrons can be controlled, and the holes can be efficiently blocked. This allows the OLED to have a long lifespan.

[0088] The electron transport layer of the organic electronic device can comprise an organic electron transport matrix material (ETM material). Furthermore, the electron transport layer can comprise one or more n-type dopants. Suitable compounds for the ETM are not particularly limited. In one embodiment, the electron transport matrix compounds consist 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 can be contained in aromatic or heteroaromatic structural units, as disclosed, for example, in documents EP 1 970 371 A1.

[0089] In one embodiment, the electron transport layer can be electrically doped with an n-type dopant. In another embodiment, the electron transport layer can comprise a second electron transport sublayer, which is located closer to the cathode than the first electron transport sublayer, and only the second electron transport sublayer can comprise the n-type dopant.

[0090] The electrical n-doping material can be selected from electropositive elemental metals and / or from 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)

[0091] 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-hydroxyquinoline oleate (LiQ), LiF, NaCl, CsF, Li₂O, BaO, Ca, Ba, Yb, and Mg, which are known in the field.

[0092] The thickness of the EIL can range from approximately 0.1 nm to approximately 10 nm, for example, from approximately 0.5 nm to approximately 9 nm. If the thickness of the EIL is within this range, the EIL can exhibit satisfactory electron injection properties without a significant loss in the drive voltage. cathode electrode

[0093] The cathode electrode is formed on the EIL, if present. The cathode electrode can be made of 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 made 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), or the like.

[0094] Alternatively, the cathode electrode can be made of a transparent conductive oxide, such as ITO or IZO.

[0095] The thickness of the cathode electrode can range from approximately 5 nm to approximately 1000 nm, for example, from approximately 10 nm to approximately 100 nm. If the thickness of the cathode electrode is in the range of approximately 5 nm to approximately 50 nm, the cathode electrode can be transparent or semi-transparent, even if it is made of a metal or metal alloy.

[0096] It is understood that the cathode electrode is not part of an electron injection layer or the electron transport layer. Charge generation layer / hole generation layer

[0097] The charge-generating layer (CGL) can consist of a bilayer. If the charge-generating layer is a p-type charge-generating layer (hole-generating layer), it can include the first compound of formula (I) as defined here.

[0098] Typically, the charge-generating layer is a pn junction connecting 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 layer adjacent to the anode. Similarly, the p-side of the pn junction generates holes and injects them into the layer adjacent to the cathode.

[0099] Charge generation layers are used in tandem devices, for example in tandem OLEDs, which include two or more emission layers between two electrodes. In a tandem OLED with two emission layers, the n-type charge generation layer provides electrons for the first emission layer, which is located near the anode, while the hole generation layer provides holes for the second emission layer, which is located between the first emission layer and the cathode.

[0100] According to the invention, the organic electronic device may comprise a hole injection layer and a hole generation layer. If a layer other than the hole generation layer comprises the first compound of formula (I) as defined herein, it is not necessary for the hole generation layer to also comprise the first compound of formula (I) as defined herein. In such a case, the hole generation layer may consist of an organic matrix material doped with a p-type dopant. Suitable matrix materials for the hole generation layer may be materials conventionally used as hole injection and / or hole transport matrix materials. A p-type dopant used for the hole generation layer may also be a conventional material.For example, the p-type dopant can be one selected from a group consisting of tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ), tetracyanoquinodimethane derivatives, radialene derivatives, iodine, FeCl3, FeF3, and SbCl5. The host can also 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).

[0101] In one embodiment, the hole-generating layer comprises the 1,3,5-trioxatriborane-containing compound as defined here, as defined in detail above.

[0102] The n-type charge-generating layer can be a layer of pure n-doper, for example, an electropositive metal, or it can consist of an organic matrix material doped with the n-doper. In one embodiment, the n-type doper 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 the group consisting of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, La, Ce, Sm, Eu, Tb, Dy, and Yb. In particular, the n-type doper can be one selected from the group consisting of Cs, K, Rb, Mg, Na, Ca, Sr, Eu, and Yb. Suitable matrix materials for the electron-generating layer can be those conventionally used as matrix materials for electron injection or electron transport layers.The matrix material can, for example, be one selected from a group consisting of triazine compounds, hydroxyquinoline derivatives such as tris(8-hydroxyquinoline)aluminium, benzazole derivatives and silo derivatives.

[0103] In one embodiment, the p-type charge-generating layer can include compounds of the following chemical formula X, where each of A 1 to A 6 Hydrogen, a halogen atom, nitrile (-CN), nitro (-NO2), sulfonyl (-SO2R), sulfoxide (-SOR), sulfonamide (-SO2NR2), sulfonate (-SO3R), trifluoromethyl (-CF3), ester (-COOR), amide (-CONHR or -CONRR'), substituted or unsubstituted straight-chain or branched-chain C1-C 12 -Alkoxy, substituted or unsubstituted straight-chain or branched-chain C1-C 12 -Alkyl, substituted or unsubstituted straight-chain or branched-chain C2-C 12-Alkenyl, a substituted or unsubstituted aromatic or non-aromatic heteroring, a substituted or unsubstituted aryl, a substituted or unsubstituted mono- or diarylamine, a substituted or unsubstituted aralkylamine, or the like. Herein, any of the foregoing R and R' may be a substituted or unsubstituted C1-C 60 -Alkyl, substituted or unsubstituted aryl or a substituted or unsubstituted 5- to 7-membered heteroring or the like.

[0104] An example of such a p-type charge-generating layer could be a layer comprising CNHAT.

[0105] The hole-generating layer can be arranged on the n-type charge-generating layer. Organic light-emitting diode (OLED)

[0106] The organic electronic device can be an organic light-emitting diode.

[0107] According to one aspect of the present invention, an organic light-emitting diode (OLED) is provided comprising: a substrate; an anode electrode formed on the substrate; a hole injection layer, a hole transport layer, an emission layer and a cathode electrode.

[0108] According to a further aspect of the present invention, an OLED is provided comprising: a substrate; an anode electrode formed on the substrate; a hole injection layer, a hole transport layer, an electron blocking layer, an emission layer, a hole blocking layer and a cathode electrode.

[0109] According to a further aspect of the present invention, an OLED is provided comprising: a substrate; an anode electrode formed on the substrate; a hole injection layer, a hole transport layer, an electron blocking layer, an emission layer, a hole blocking layer, an electron transport layer and a cathode electrode.

[0110] According to a further aspect of the present invention, an OLED is provided comprising: a substrate; an anode electrode formed on the substrate; a hole injection layer, a hole transport layer, an electron blocking layer, an emission layer, a hole blocking layer, an electron transport layer, an electron injection layer and a cathode electrode.

[0111] According to various embodiments of the present invention, OLEDs can be provided comprising layers arranged between the above-mentioned layers on the substrate or on the upper electrode.

[0112] According to one aspect, the OLED can comprise a layered substrate structure that is adjacent to an anode electrode, the anode electrode is adjacent to a first hole injection layer, the first hole injection layer is adjacent to a first hole transport layer, the first hole transport layer is adjacent to a first electron blocking layer, the first electron blocking layer is adjacent to a first emission layer, the first emission layer is adjacent to a first electron transport layer, the first electron transport layer is adjacent to an n-type charge generation layer, the n-type charge generation layer is adjacent to a hole generation layer, and the hole generation layer is 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 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.

[0113] For example, the OLED can be used according to Fig. 2 are formed by a process in which 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 subsequently formed in this order on a substrate (110). Method for manufacturing the organic electronic device

[0114] According to another aspect, the invention relates to a method for manufacturing the organic electronic device according to the present invention, wherein the method comprises a step of depositing the compound of formula (I) according to the present invention on a solid support.

[0115] The separation process may include: - Separation via thermal vacuum evaporation; - Deposition via solution processing, wherein the processing is preferably selected from rotational coating, printing, casting; and / or - Slotted nozzle coating. Display device

[0116] According to another aspect, the invention relates to a display device comprising the organic electronic device according to the invention, wherein the organic electronic device is an organic light-emitting diode.

[0117] The display device can comprise at least two organic electronic devices according to the invention, wherein the organic electronic devices are each organic light-emitting diodes. Combination of formula (Ib)

[0118] According to another aspect, the invention relates to a compound with formula (Ib)

[0119] In formula (Ib) R 1 to R 4 independently selected from the group consisting of F, halogen-substituted C1- to C 12 -Alkyl and H, wherein at least two of R 1 to R 4 are selected from F and halogen-substituted C1 to C 12 -Alkyl. R 1 to R 4 can be independently selected from the group consisting of F, halogen-substituted C1 to C4 alkyl and H, wherein at least two of R 1 to R 4 Selected are from F and halogen-substituted C1bisC4 alkyl. R 1 to R 4may be independently selected from the group consisting of F, fully halogen-substituted C1- to C4-alkyl and H, wherein at least two of R 1 to R 4 The selected compounds are F and fully halogen-substituted C1 to C4 alkyl. In this context, "fully substituted" means that each hydrogen atom of the respective alkyl group is replaced by a halogen atom. R 1 to R 4 can be independently selected from the group consisting of F, F-substituted C1 to C4 alkyl and H, wherein at least two of R 1 to R 4 are selected from F and F-substituted C1- to C4-alkyl. R 1 to R 4 can be independently selected from the group consisting of F, fully F-substituted C1bisC4 alkyl and H, wherein at least two of R 1 to R 4 are selected from F and fully F-substituted C1- to C4-alkyl. R 1 to R 4can be independently selected from the group consisting of F, CF3 and H, where at least two of R 1 to R 4 Selected are from F and CF3. R 1 to R 4 can be independently selected from the group consisting of F and H, where at least two of R 1 to R 4 F are.

[0120] In formula (Ib) R 1' to R 4' independently selected from the group consisting of F, halogen-substituted C1- to C 12 -Alkyl and H, wherein at least two of R 1' to R 4' are selected from F and halogen-substituted C1 to C 12 -Alkyl. R 1' to R 4' can be independently selected from the group consisting of F, halogen-substituted C1 to C4 alkyl and H, wherein at least two of R 1' to R 4' are selected from F and halogen-substituted C1- to C4-alkyl. R 1' to R 4'may be independently selected from the group consisting of F, fully halogen-substituted C1- to C4-alkyl and H, wherein at least two of R 1' to R 4' The selected compounds are F and fully halogen-substituted C1 to C4 alkyl. In this context, "fully substituted" means that each hydrogen atom of the respective alkyl group is replaced by a halogen atom. R 1' to R 4' can be independently selected from the group consisting of F, F-substituted C1 to C4 alkyl and H, wherein at least two of R 1' to R 4' are selected from F and F-substituted C1- to C4-alkyl. R 1' to R 4' can be independently selected from the group consisting of F, fully F-substituted C1- to C4-alkyl and H, wherein at least two of R 1' to R 4' are selected from F and fully F-substituted C1- to C4-alkyl. R 1' to R 4'can be independently selected from the group consisting of F, CF3 and H, where at least two of R 1 ' to R 4 ' selected from F and CF3. R 1 ' to R 4 ' can be independently selected from the group consisting of F and H, where at least two are from R 1 ' to R 4 'F are.

[0121] It may be provided that R 1 to R 4 and R 1 ' to R 4 ' are independently selected from F, CN or CF3; or - R 1 to R 3 and R 2 ' to R 4 ' are F, independently selected from F, CN or CF3, and R 4 and R 1 ' are H; or - R 2 , R 3 , R 2 ' and R 3 ' are independently selected from F, CN or CF3, and R 1 ; R 4 , R 1 ' and R 4 ' are H.

[0122] It may be provided that R 1 to R 4 and R 1 ' to R 4 ' are F; or - R 1 to R 3 and R 2 ' to R 4 'are F, and R 4 and R 1 ' are H; or - R 2 , R 3 , R 2 ' and R 3 ' are F, and R 1 ; R 4 , R 1 ' and R 4 ' are H.

[0123] It may be provided that R 2 , R 3 , R 2 ' and R 3 ' are independently selected from F, CN or CF3 and R 1 ; R 4 , R 1 ' and R 4 ' are H.

[0124] It may be provided that R 2 , R 3 , R 2 ' and R 3 ' are F; and R 1 ; R 4 , R 1 ' and R 4 ' are H.

[0125] Ar 1 and Ar 2are independently selected from the group consisting of substituted C6 to C 18 -Aryl (such as phenyl, 1,1'-biphenyl-4-yl, naphthyl, anthracenyl, phenanthrenyl), unsubstituted C2- to C 17 -Heteroaryl (such as triazine, diazine, pyrazine, pyrimidine, pyridine, quinazoline or benzoquinazoline) and substituted C2- to C 17 -Heteroaryl (such as triazine, diazine, pyrazine, pyrimidine, pyridine, quinazoline or benzoquinazoline). Ar 1 and Ar 2 can be independently selected from the group consisting of substituted C6 to C 12 -Aryl, unsubstituted C2- to C 11 -Heteroaryl and substituted C2- to C 11 -Heteroaryl. Ar 1 and Ar 2 can be independently selected from the group consisting of substituted phenyl, unsubstituted C3- to C5-heteroaryl, and substituted C3- to C5-heteroaryl. Ar 1 and Ar 2They can be independently selected from the group consisting of substituted phenyl, unsubstituted pyridyl, and substituted pyridyl. In all cases, it is stipulated that at least one of the substituents of the substituted C6 to C 18 -Aryls is selected from the group consisting of CN and halogen-substituted C1- to C 12 -Alkyl.

[0126] Ar 1 and Ar 2 can be independently selected from the group consisting of C6 to C 18 -Aryl, substituted with at least three substituents, unsubstituted C2- to C 17 -Heteroaryl and C2- to C 17 -Heteroaryl, substituted with at least three substituents. Ar 1 and Ar 2 can be independently selected from the group consisting of C6 to C 12 -Aryl, substituted with at least three substituents, unsubstituted C2- to C 11 -Heteroaryl and C2- to C 11-Heteroaryl, substituted with at least three substituents. Ar 1 and Ar 2 can be independently selected from the group consisting of phenyl substituted with at least three substituents, unsubstituted C3- to C5-heteroaryl, and C3- to C5-heteroaryl substituted with at least three substituents. 1 and Ar 2 They can be independently selected from the group consisting of phenyl substituted with at least three substituents, unsubstituted pyridyl, and pyridyl substituted with at least three substituents. In all cases, it is stipulated that at least one of the substituents of the substituted C6 to C 18 -Aryls is selected from the group consisting of CN and halogen-substituted C1- to C 12 -Alkyl.

[0127] Ar 1 and Ar 2 can be independently selected from the group consisting of fully substituted C6 to C 18 -Aryl, unsubstituted C2- to C17 -Heteroaryl and fully substituted C2- to C 17 -Heteroaryl. Ar 1 and Ar 2 can be independently selected from the group consisting of fully substituted C6 to C 12 -Aryl, unsubstituted C2- to C 11 -Heteroaryl and fully substituted C2- to C 11 -Heteroaryl. Ar 1 and Ar 2 can be independently selected from the group consisting of fully substituted phenyl, unsubstituted C3- to C5-heteroaryl, and fully substituted C3- to C5-heteroaryl. Ar 1 and Ar 2 They can be independently selected from the group consisting of fully substituted phenyl, unsubstituted pyridyl, and fully substituted pyridyl. In all cases, it is stipulated that at least one of the substituents of the substituted C6 to C 18 -Aryls is selected from the group consisting of CN and halogen-substituted C1- to C 12-Alkyl.

[0128] In the event that Ar 1 and / or Ar 2 substituted C6 to C 18 -Aryl is / are (including any of the aforementioned respective restricted embodiments), is / are one or more substituents independently selected from the group consisting of halogen, CN and halogen-substituted C1- to C 12 -Alkyl, wherein at least one of the substituents of the substituted C6- to C 18 -Aryls is selected from the group consisting of CN and halogen-substituted C1- to C 12 -Alkyl. In the event that Ar 1 and / or Ar 2 substituted C6-bis C 18 -Aryl is / are (including any of the aforementioned respective restricted embodiments), is / are one or more substituents independently selected from the group consisting of F, Cl, Br, I, CN, F-substituted C1- to C 12 -Alkyl, Cl-substituted C1- to C 12-Alkyl, Br-substituted C1- to C 12 -Alkyl and I-substituted C1bis C 12 -Alkyl, wherein at least one of the substituents of the substituted C6- to C 18 -Aryls is selected from the group consisting of CN, F-substituted C1- to C 12 -Alkyl, Cl-substituted C1- to C 12 -Alkyl, Br-substituted C1- to C 12 -Alkyl and I-substituted C1bis C 12 -Alkyl. In the event that Ar 1 and / or Ar 2 substituted C6 to C 18 -Aryl is / are (including any of the aforementioned respective restricted embodiments), is / are one or more substituents independently selected from the group consisting of F, CN and F-substituted C1- to C 12 -Alkyl, wherein at least one of the substituents of the substituted C6- to C 18 -Aryls is selected from the group consisting of CN and F-substituted C1- to C 12 -Alkyl.

[0129] In the event that Ar 1 and / or Ar 2 substituted C6 to C 18 -Aryl is / are (including any of the aforementioned respective restricted embodiments), the one or more substituents are independently selected from the group consisting of halogen, CN and halogen-substituted C1- to C4-alkyl, wherein at least one of the substituents of the substituted C6- to C 18 -Aryls is selected from the group consisting of CN and halogen-substituted C1- to C4-alkyl. In the event that Ar 1 and / or Ar 2 substituted C6bis C 18 -Aryl is / are (including any of the aforementioned respective restricted embodiments), is / are one or more substituents independently selected from the group consisting of F, Cl, Br, I, CN, F-substituted C1- to C4-alkyl, Cl-substituted C1- to C 12-Alkyl, Br-substituted C1- to C4-alkyl and I-substituted C1bis C4-alkyl, wherein at least one of the substituents of the substituted C6- to C 18 -Aryls is selected from the group consisting of CN, F-substituted C1- to C4-alkyl, Cl-substituted C1- to C 12 -Alkyl, Br-substituted C1- to C4-alkyl, and I-substituted C1- to C4-alkyl. In the event that Ar 1 and / or Ar 2 substituted C6 to C 18 -Aryl is / are (including any of the aforementioned respective restricted embodiments), is / are one or more substituents independently selected from the group consisting of F, CN and F-substituted C1- to C4-alkyl, wherein at least one of the substituents of the substituted C6- to C 18 -Aryls is selected from the group consisting of CN and F-substituted C1- to C4-alkyl.

[0130] In the event that Ar 1 and / or Ar 2substituted C6 to C 18 -Aryl is / are (including any of the aforementioned respective restricted embodiments), is / are one or more substituents independently selected from the group consisting of halogen, CN and fully halogen-substituted C1- to C4-alkyl, wherein at least one of the substituents of the substituted C6- to C 18 -Aryls is selected from the group consisting of CN and fully halogen-substituted C1- to C4-alkyl. In the event that Ar 1 and / or Ar 2 substituted C6 to C 18 -Aryl is / are (including any of the aforementioned respective restricted embodiments), is / are one or more substituents independently selected from the group consisting of F, Cl, Br, I, CN, fully F-substituted C1- to C4-alkyl, fully Cl-substituted C1- to C 12-Alkyl, fully Br-substituted C1- to C4-alkyl and fully I-substituted C1- to C4-alkyl, wherein at least one of the substituents of the substituted C6- to C 18 -Aryls is selected from the group consisting of CN, fully F-substituted C1- to C4-alkyl, fully Cl-substituted C1- to C 12 -Alkyl, fully Br-substituted C1- to C4-alkyl, and fully I-substituted C1- to C4-alkyl. In the event that Ar 1 and / or Ar 2 substituted C6 to C 18 -Aryl is / are (including any of the aforementioned respective restricted embodiments), is / are one or more substituents independently selected from the group consisting of F, CN and fully F-substituted C1- to C4-alkyl 1, wherein at least one of the substituents of the substituted C6- to C 18-Aryls is selected from the group consisting of CN and fully F-substituted C1- to C4-alkyl. In the event that Ar 1 and / or Ar 2 substituted C6 to C 18 -Aryl is / are (including any of the aforementioned respective restricted embodiments), is / are one or more substituents independently selected from the group consisting of F, CN and CF3, wherein at least one of the substituents of the substituted C6- to C 18 -Aryls is selected from the group consisting of CN and CF3.

[0131] In the event that Ar 1 and / or Ar 2 substituted C6 to C 18 -Aryl is / are, the respective substituted C6- to C 18 -Aryl independent Fully substituted phenyl, wherein the substituents are independently selected from F, CN and CF3, preferably the substituents in the 2, 3, 5 and 6 positions of the phenyl are each F and the substituent in the 4 position of the phenyl is CF3 or CN; or 2,4,6-substituted phenyl, wherein the substituent at the 2-position of the phenyl, the substituent at the 4-position of the phenyl and the substituent at the 6-position of the phenyl are independently selected from the group consisting of F, CN and CF3, wherein at least one of the substituents of the substituted C6- to C 18 -Aryls is selected from the group consisting of CN and CF3, preferably the substituents are independently selected from CN and CF3.

[0132] It may be provided that - at least one, preferably both, of Ar 1 and Ar 2 independently selected from the group consisting of substituted C6 to C18 -Aryl; and - the substituted C6 to C 18 -Aryl is substituted with at least one substituent independently selected from the group consisting of halogen, CN and halogen-substituted C1- to C 12 -Alkyl, wherein at least one of the substituents is selected from the group consisting of CN and halogen-substituted C1- to C 12 -Alkyl.

[0133] It may be provided that - at least one, preferably both, of Ar 1 and Ar 2 independently selected from the group consisting of substituted C6 to C 18 -Aryl; and - the substituted C6 to C 18 -Aryl is substituted with at least one substituent which is independently selected from the group consisting of F, CN and CF3, wherein at least one of the substituents is selected from the group consisting of CN and CF3.

[0134] In the event that Ar1 and / or Ar 2 substituted C2- to C 17 -Heteroaryl is / are (including any of the aforementioned respective restricted embodiments), is / are one or more substituents independently selected from the group consisting of halogen, CN and halogen-substituted C1- to C 12 -Alkyl. In the event that Ar 1 and / or Ar 2 substituted C2- to C 17 -Heteroaryl is / are (including any of the aforementioned respective restricted embodiments), is / are one or more substituents independently selected from the group consisting of F, Cl, Br, I, CN, F-substituted C1bis C 12 -Alkyl, Cl-substituted C1- to C 12 -Alkyl, Br-substituted C1- to C 12 -Alkyl and I-substituted C1- to C 12 -Alkyl. In the event that Ar 1 and / or Ar 2 substituted C2- to C 17-Heteroaryl is / are (including any of the aforementioned respective restricted embodiments), is / are one or more substituents independently selected from the group consisting of F, CN and F-substituted C1- to C 12 -Alkyl.

[0135] In the event that Ar 1 and / or Ar 2 substituted C2- to C 17 -Heteroaryl is / are (including any of the aforementioned respective restricted embodiments), is / are one or more substituents independently selected from the group consisting of halogen, CN, and halogen-substituted C1- to C4-alkyl. In the event that Ar 1 and / or Ar 2 substituted C2- to C 17-Heteroaryl is / are (including any of the aforementioned respective restricted embodiments), is / are one or more substituents independently selected from the group consisting of F, Cl, Br, I, CN, F-substituted C1 to C4 alkyl, Cl-substituted C1 to C 12 -Alkyl, Br-substituted C1- to C4-alkyl, and I-substituted C1- to C4-alkyl. In the event that Ar 1 and / or Ar 2 substituted C2- to C 17 -Heteroaryl is / are (including any of the aforementioned respective restricted embodiments), is / are one or more substituents independently selected from the group consisting of F, CN and F-substituted C1- to C4-alkyl.

[0136] In the event that Ar 1 and / or Ar 2 substituted C2- to C 17-Heteroaryl is / are (including any of the aforementioned respective restricted embodiments), is / are one or more substituents independently selected from the group consisting of halogen, CN, and fully halogen-substituted C1- to C4-alkyl. In the event that Ar 1 and / or Ar 2 substituted C2- to C 17 -Heteroaryl is / are (including any of the aforementioned respective restricted embodiments), is / are one or more substituents independently selected from the group consisting of F, Cl, Br, I, CN, fully F-substituted C1- to C4-alkyl, fully Cl-substituted C1- to C 12 -Alkyl, fully Br-substituted C1- to C4-alkyl, and fully I-substituted C1- to C4-alkyl. In the event that Ar 1 and / or Ar 2 substituted C2- to C 17-Heteroaryl is / are (including any of the aforementioned respective restricted embodiments), is / are one or more substituents independently selected from the group consisting of F, CN and fully F-substituted C1- to C4-alkyl. In the event that Ar 1 and / or Ar 2 substituted C2- to C 17 -Heteroaryl is / are (including any of the aforementioned respective restricted embodiments), is / are one or more substituents independently selected from the group consisting of F, CN and CF3. In the event that Ar 1 and / or Ar 2 substituted C2- to C 17 -Heteroaryl is / are (including any of the aforementioned respective restricted embodiments), is / are the one or more substituents F.

[0137] It may be provided that in formula (Ib) Ar 1 selected from groups of the following structures Ar1 -1 to Ar 1 -5 where the respective structure is bound to *1 in order to

[0138] It may be provided that in formula (Ib) Ar 2 selected from groups of the following structures Ar 2 -1 to Ar 2 -5 where the respective structure is bound to *2 in order to

[0139] It may be provided that Ar 1 and Ar 2 are selected the same way.

[0140] The combination of formula (Ib) can be selected from E1 to E10. Use of the compounds of formulas (I) and (Ib)

[0141] According to another aspect, the invention relates to a use of the compound according to the invention with formula (I) or the compound according to the invention with formula (Ib) as a p-doping agent in an organic semiconductor material or in a hole injection layer.

[0142] The compound according to the invention with formula (I) or the compound according to formula (Ib) can be used as the predominant material in the electron injection layer. The hole injection layer can consist essentially of the compound according to formula (I) or the compound according to formula (Ib). The fact that the hole injection layer in this alternative consists of the compound according to formula (I) or the compound according to formula (Ib) does not preclude impurities. Impurities have no technical effect with regard to the problem solved by the present invention. Impurities are not intentionally added to the layer during processing.

[0143] Alternatively, the compound according to the invention with formula (I) or the compound according to the invention with formula (Ib) can be used together with at least one further compound (second compound) as a p-doping agent. The second compound can be a hole transport matrix compound, in particular an organic hole transport matrix compound.

[0144] The organic hole transport matrix compound can comprise a conjugated system of at least 6 delocalized electrons, alternatively at least 10 delocalized electrons, or alternatively at least 14 delocalized electrons.

[0145] The organic hole transport matrix compound can be selected from organic compounds comprising at least one amine nitrogen substituted with groups independently selected from C6 to C6. 42 -Aryl and C3- to C 42 -Heteroaryl.

[0146] Examples of the second compound that can be used to form the semiconductor layer together with the first compound 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'-diphenylbenzidine (alpha-NPD); and triphenylamine-based compounds, such as 4,4',4''-tris(N-carbazolyl)triphenylamine (TCTA).

[0147] The compound according to the invention with formula (I) or the compound according to formula (Ib) can be used as a p-doping agent in a material in an amount of less than 50 wt.%, based on the total weight of the material, together with at least one other compound. The compound according to the invention with formula (I) or the compound according to formula (Ib) can be used as a p-doping agent in a material in an amount of less than 40 wt.%, based on the total weight of the material, together with at least one other compound. The compound according to the invention with formula (I) or the compound according to formula (Ib) can be used as a p-doping agent in a material in an amount of less than 30 wt.%, based on the total weight of the material, together with at least one other compound.The compound according to the invention with formula (I) or the compound according to formula (Ib) can be used as a p-doping agent in a material in an amount of less than 20 wt.%, based on the total weight of the material, together with at least one other compound. The compound according to the invention with formula (I) or the compound according to formula (Ib) can be used as a p-doping agent in a material in an amount of less than 15 wt.%, based on the total weight of the material, together with at least one other compound. The compound according to the invention with formula (I) or the compound according to formula (Ib) can be used as a p-doping agent in a material in an amount of less than 10 wt.%, based on the total weight of the material, together with at least one other compound.The compound according to the invention with formula (I) or the compound according to the invention with formula (Ib) can be used as a p-doping agent in a material in an amount of less than 5 wt.%, based on the total weight of the material, together with at least one other compound.

[0148] The compound according to the invention with formula (I) or the compound according to formula (Ib) can be used as a p-doping agent in a material in an amount of 0.01 to 50 wt.%, based on the total weight of the material, together with at least one other compound. The compound according to the invention with formula (I) or the compound according to formula (Ib) can be used as a p-doping agent in a material in an amount of 0.05 to 40 wt.%, based on the total weight of the material, together with at least one other compound. The compound according to formula (I) or the compound according to formula (Ib) can be used as a p-doping agent in a material in an amount of 0.1 to 30 wt.%, based on the total weight of the material, together with at least one other compound.The compound according to the invention with formula (I) or the compound according to formula (Ib) can be used as a p-doping agent in a material in an amount of 0.5 to 20 wt.%, based on the total weight of the material, together with at least one other compound. The compound according to the invention with formula (I) or the compound according to formula (Ib) can be used as a p-doping agent in a material in an amount of 1 to 10 wt.%, based on the total weight of the material, together with at least one other compound. The compound according to formula (I) or the compound according to formula (Ib) can be used as a p-doping agent in a material in an amount of 1 to 5 wt.%, based on the total weight of the material, together with at least one other compound.The compound according to the invention with formula (I) or the compound according to the invention with formula (Ib) can be used as a p-doping agent in a material in an amount of 1 to 3 wt.%, such as about 2 wt.%, based on the total weight of the material, together with at least one other compound. Method for the preparation of the compound of formula (I) and (Ib)

[0149] According to a further aspect, the invention relates to a method for producing a compound of formula (I) (compounds of formula (Ib) can be produced in the same way), wherein the method comprises a step of Converting a compound of formula (II) with a compound of formula (III) and with a compound of formula (IV) M 1 -Ar 1 (III) M 2 -Ar 2 (IV) or with a combination of the formula (V) Ar 1 -M 3 -Ar2 (V) to obtain the connection of formula (Ib)

[0150] In formula (II) R 1 to R 4 independently selected from the group consisting of F, halogen-substituted C1- to C 12 -Alkyl and H, wherein at least two of R 1 to R 4 from F and halogen-substituted C1 to C 12 -Alkyl are selected. R 1 to R 4 can be independently selected from the group consisting of F, halogen-substituted C1 to C4 alkyl and H, wherein at least two of R 1 to R 4 Selected are from F and halogen-substituted C1bisC4 alkyl. R 1 to R 4 may be independently selected from the group consisting of F, fully halogen-substituted C1- to C4-alkyl and H, wherein at least two of R 1 to R 4The selected compounds are F and fully halogen-substituted C1 to C4 alkyl. In this context, "fully substituted" means that each hydrogen atom of the respective alkyl group is replaced by a halogen atom. R 1 to R 4 can be independently selected from the group consisting of F, F-substituted C1 to C4 alkyl and H, wherein at least two of R 1 to R 4 are selected from F and F-substituted C1- to C4-alkyl. R 1 to R 4 can be independently selected from the group consisting of F, fully F-substituted C1bisC4 alkyl and H, wherein at least two of R 1 to R 4 are selected from F and fully F-substituted C1- to C4-alkyl. R 1 to R 4 can be independently selected from the group consisting of F, CF3 and H, where at least two of R 1 to R 4 Selected are from F and CF3. R 1 to R 4can be independently selected from the group consisting of F and H, where at least two of R 1 to R 4 F are.

[0151] In formula (II) R 1 ' to R 4 ' independently selected from the group consisting of F, halogen-substituted C1- to C 12 -Alkyl and H, wherein at least two of R 1 ' to R 4 ' are selected from F and halogen-substituted C1 to C 12 -Alkyl. R 1 ' to R 4 ' can be independently selected from the group consisting of F, halogen-substituted C1- to C 12 -Alkyl and H, wherein at least two of R 1 ' to R 4 ' are selected from F and halogen-substituted C1 to C 12 -Alkyl. R 1 ' to R 4 ' can be independently selected from the group consisting of F, fully halogen-substituted C1- to C4-alkyl and H, wherein at least two of R 1 ' to R 4' are selected from F and fully halogen-substituted C1 to C4 alkyl. In this respect, "fully substituted" means that each hydrogen atom of the respective alkyl group is replaced by a halogen atom. R 1 ' to R 4 ' can be independently selected from the group consisting of F, F-substituted C1 to C4 alkyl and H, wherein at least two of R 1 ' to R 4 ' are selected from F and F-substituted C1- to C4-alkyl. R 1 ' to R 4 ' can be independently selected from the group consisting of F, fully F-substituted C1- to C4-alkyl and H, wherein at least two of R 1 ' to R 4 ' are selected from F and fully F-substituted C1- to C4-alkyl. R 1 ' to R 4 ' can be independently selected from the group consisting of F, CF3 and H, where at least two of R 1 ' to R 4 ' selected from F and CF3. R 1 ' to R4 ' can be independently selected from the group consisting of F and H, where at least two are from R 1 ' to R 4 'F are.

[0152] It may be provided that - R 1 to R 4 and R 1 ' to R 4 ' are independently selected from F, CN or CF3; or - R 1 to R 3 and R 2 ' to R 4 ' are F, independently selected from F, CN or CF3, and R 4 and R 1 ' are H; or - R 2 , R 3 , R 2 ' and R 3 ' are independently selected from F, CN or CF3, and R 1 ; R 4 , R 1 ' and R 4 ' are H.

[0153] It may be provided that - R 1 to R 4 and R 1 ' to R 4 ' are F; or - R 1 to R 3 and R 2 ' to R4 ' are F, and R 4 and R 1 ' are H; or - R 2 , R 3 , R 2 ' and R 3 ' are F, and R 1 ; R 4 , R 1 ' and R 4 ' are H.

[0154] It may be provided that R 2 , R 3 , R 2 ' and R 3 ' are independently selected from F, CN or CF3 and R 1 ; R 4 , R 1 ' and R 4 ' are H.

[0155] It may be provided that R 2 , R 3 , R 2 ' and R 3 ' are F; and R 1 ; R 4 , R 1 ' and R 4 ' are H.

[0156] Ar 1 in formula (III) and Ar 2 in formula (IV) are independently selected from the group consisting of substituted C6- to C 18-Aryl (such as phenyl, 1,1'-biphenyl-4-yl, naphthyl, anthracenyl, phenanthrenyl), unsubstituted C2- to C 17 -Heteroaryl (such as triazine, diazine, pyrazine, pyrimidine, pyridine, quinazoline or benzoquinazoline) and substituted C2- to C 17 -Heteroaryl (such as triazine, diazine, pyrazine, pyrimidine, pyridine, quinazoline or benzoquinazoline). Ar 1 and Ar 2 can be independently selected from the group consisting of substituted C6 to C 12 -Aryl, unsubstituted C2- to C 11 -Heteroaryl and substituted C2- to C 11 -Heteroaryl. Ar 1 and Ar 2 can be independently selected from the group consisting of substituted phenyl, unsubstituted C3- to C5-heteroaryl, and substituted C3- to C5-heteroaryl. Ar 1 and Ar 2 can be independently selected from the group consisting of substituted phenyl, unsubstituted pyridyl and substituted pyridyl.

[0157] Ar 1 in formula (III) and Ar 2 in formula (IV) can be independently selected from the group consisting of C6 to C 18 -Aryl, substituted with at least three substituents, unsubstituted C2- to C 17 -Heteroaryl and C2- to C 17 -Heteroaryl, substituted with at least three substituents. Ar 1 and Ar 2 can be independently selected from the group consisting of C6 to C 12 -Aryl, substituted with at least three substituents, unsubstituted C2- to C 11 -Heteroaryl and C2- to C 11 -Heteroaryl, substituted with at least three substituents. Ar 1 and Ar 2 can be independently selected from the group consisting of phenyl substituted with at least three substituents, unsubstituted C3- to C5-heteroaryl, and C3- to C5-heteroaryl substituted with at least three substituents. 1 and Ar 2can be independently selected from the group consisting of phenyl substituted with at least three substituents, unsubstituted pyridyl and pyridyl substituted with at least three substituents.

[0158] Ar 1 in formula (III) and Ar 2 in formula (IV) can be independently selected from the group consisting of fully substituted C6- to C 18 -Aryl, unsubstituted C2- to C 17 -Heteroaryl and fully substituted C2- to C 17 -Heteroaryl. Ar 1 and Ar 2 can be independently selected from the group consisting of fully substituted C6 to C 12 -Aryl, unsubstituted C2- to C 11 -Heteroaryl and fully substituted C2- to C 11 -Heteroaryl. Ar 1 and Ar 2can be independently selected from the group consisting of fully substituted phenyl, unsubstituted C3- to C5-heteroaryl, and fully substituted C3- to C5-heteroaryl. Ar 1 and Ar 2 can be independently selected from the group consisting of fully substituted phenyl, unsubstituted pyridyl and fully substituted pyridyl.

[0159] In the event that Ar 1 and / or Ar 2 substituted C6 to C 18 -Aryl is / are (including any of the aforementioned respective restricted embodiments), is / are one or more substituents independently selected from the group consisting of halogen, CN and halogen-substituted C1- to C 12 -Alkyl, wherein at least one of the substituents of the substituted C6- to C 18 -Aryls is selected from the group consisting of CN and halogen-substituted C1- to C 12 -Alkyl. In the event that Ar1 and / or Ar 2 substituted C6bis C 18 -Aryl is / are (including any of the aforementioned respective restricted embodiments), is / are one or more substituents independently selected from the group consisting of F, Cl, Br, I, CN, F-substituted C1- to C 12 -Alkyl, Cl-substituted C1- to C 12 -Alkyl, Br-substituted C1- to C 12 -Alkyl and I-substituted C1bis C 12 -Alkyl, wherein at least one of the substituents of the substituted C6- to C 18 -Aryls is selected from the group consisting of CN and F-substituted C1- to C 12 -Alkyl, Cl-substituted C1- to C 12 -Alkyl, Br-substituted C1- to C 12 -Alkyl and I-substituted C1bis C 12 -Alkyl. In the event that Ar 1 and / or Ar 2 substituted C6 to C 18-Aryl is / are (including any of the aforementioned respective restricted embodiments), is / are one or more substituents independently selected from the group consisting of F, CN and F-substituted C1- to C 12 -Alkyl, wherein at least one of the substituents of the substituted C6- to C 18 -Aryls is selected from the group consisting of CN and F-substituted C1- to C 12 -Alkyl.

[0160] In the event that Ar 1 and / or Ar 2 substituted C6 to C 18 -Aryl is / are (including any of the aforementioned respective restricted embodiments), the one or more substituents are independently selected from the group consisting of halogen, CN and halogen-substituted C1- to C4-alkyl, wherein at least one of the substituents of the substituted C6- to C 18-Aryls is selected from the group consisting of CN and halogen-substituted C1- to C4-alkyl. In the event that Ar 1 and / or Ar 2 substituted C6bis C 18 -Aryl is / are (including any of the aforementioned respective restricted embodiments), is / are one or more substituents independently selected from the group consisting of F, Cl, Br, I, CN, F-substituted C1- to C4-alkyl, Cl-substituted C1- to C 12 -Alkyl, Br-substituted C1- to C4-alkyl and I-substituted C1bis C4-alkyl, wherein at least one of the substituents of the substituted C6- to C 18 -Aryls is selected from the group consisting of CN and F-substituted C1- to C4-alkyl, Cl-substituted C1- to C 12 -Alkyl, Br-substituted C1- to C4-alkyl, and I-substituted C1- to C4-alkyl. In the event that Ar 1 and / or Ar 2 substituted C6 to C 18-Aryl is / are (including any of the aforementioned respective restricted embodiments), is / are one or more substituents independently selected from the group consisting of F, CN and F-substituted C1- to C4-alkyl, wherein at least one of the substituents of the substituted C6- to C 18 -Aryls is selected from the group consisting of CN and F-substituted C1- to C4-alkyl.

[0161] In the event that Ar 1 and / or Ar 2 substituted C6 to C 18 -Aryl is / are (including any of the aforementioned respective restricted embodiments), is / are one or more substituents independently selected from the group consisting of halogen, CN and fully halogen-substituted C1- to C4-alkyl, wherein at least one of the substituents of the substituted C6- to C 18-Aryls is selected from the group consisting of CN and fully halogen-substituted C1- to C4-alkyl. In the event that Ar 1 and / or Ar 2 substituted C6 to C 18 -Aryl is / are (including any of the aforementioned respective restricted embodiments), is / are one or more substituents independently selected from the group consisting of F, Cl, Br, I, CN, fully F-substituted C1- to C4-alkyl, fully Cl-substituted C1- to C 12 -Alkyl, fully Br-substituted C1- to C4-alkyl and fully I-substituted C1- to C4-alkyl, wherein at least one of the substituents of the substituted C6- to C 18 -Aryls is selected from the group consisting of CN and fully F-substituted C1- to C4-alkyl, fully Cl-substituted C1- to C 12 -Alkyl, fully Br-substituted C1- to C4-alkyl, and fully I-substituted C1- to C4-alkyl. In the event that Ar1 and / or Ar 2 substituted C6 to C 18 -Aryl is / are (including any of the aforementioned respective restricted embodiments), is / are one or more substituents independently selected from the group consisting of F, CN and fully F-substituted C1- to C4-alkyl, wherein at least one of the substituents of the substituted C6- to C 18 -Aryls is selected from the group consisting of CN and fully F-substituted C1- to C4-alkyl. In the event that Ar 1 and / or Ar 2 substituted C6 to C 18 -Aryl is / are (including any of the aforementioned respective restricted embodiments), is / are one or more substituents independently selected from the group consisting of F, CN and CF3, wherein at least one of the substituents of the substituted C6- to C 18 -Aryls is selected from the group consisting of CN and CF3.

[0162] In the event that Ar 1 and / or Ar 2 substituted C6 to C 18 -Aryl is / are, the respective substituted C6- to C 18 -Aryl independent fully substituted phenyl, wherein the substituents are independently selected from F, CN and CF3, wherein at least one of the substituents of the substituted C6- to C 18 -Aryls is selected from the group consisting of CN and CF3, preferably the substituents in the 2, 3, 5 and 6 positions of the phenyl are F and the substituent in the 4 position of the phenyl is CF3 or CN; or 2,4,6-substituted phenyl, wherein the substituent at the 2-position of the phenyl, the substituent at the 4-position of the phenyl and the substituent at the 6-position of the phenyl are independently selected from the group consisting of F, CN and CF3, wherein at least one of the substituents of the substituted C6- to C 18-Aryls is selected from the group consisting of CN and CF3, preferably CN and CF3.

[0163] It may be provided that - at least one, preferably both, of Ar 1 and Ar 2 independently selected from the group consisting of substituted C6 to C 18 -Aryl; and - the substituted C6 to C 18 -Aryl is substituted with at least one substituent independently selected from the group consisting of halogen, CN and halogen-substituted C1- to C 12 -Alkyl, wherein at least one of the substituents is selected from the group consisting of CN and halogen-substituted C1- to C 12 -Alkyl.

[0164] It may be provided that - at least one, preferably both, of Ar 1 and Ar 2 independently selected from the group consisting of substituted C6 to C 18 -Aryl; and - the substituted C6 to C 18 -Aryl is substituted with at least one substituent which is independently selected from the group consisting of F, CN and CF3, wherein at least one of the substituents is selected from the group consisting of CN and CF3.

[0165] In the event that Ar 1 and / or Ar 2 substituted C2- to C 17 -Heteroaryl is / are (including any of the aforementioned respective restricted embodiments), is / are one or more substituents independently selected from the group consisting of halogen, CN and halogen-substituted C1- to C 12 -Alkyl. In the event that Ar 1 and / or Ar 2 substituted C2- to C 17-Heteroaryl is / are (including any of the aforementioned respective restricted embodiments), is / are one or more substituents independently selected from the group consisting of F, Cl, Br, I, CN, F-substituted C1bis C 12 -Alkyl, Cl-substituted C1- to C 12 -Alkyl, Br-substituted C1- to C 12 -Alkyl and I-substituted C1- to C 12 -Alkyl. In the event that Ar 1 and / or Ar 2 substituted C2- to C 17 -Heteroaryl is / are (including any of the aforementioned respective restricted embodiments), is / are one or more substituents independently selected from the group consisting of F, CN and F-substituted C1- to C 12 -Alkyl.

[0166] In the event that Ar 1 and / or Ar 2 substituted C2- to C 17-Heteroaryl is / are (including any of the aforementioned respective restricted embodiments), is / are one or more substituents independently selected from the group consisting of halogen, CN, and halogen-substituted C1- to C4-alkyl. In the event that Ar 1 and / or Ar 2 substituted C2- to C 17 -Heteroaryl is / are (including any of the aforementioned respective restricted embodiments), is / are one or more substituents independently selected from the group consisting of F, Cl, Br, I, CN, F-substituted C1 to C4 alkyl, Cl-substituted C1 to C 12 -Alkyl, Br-substituted C1- to C4-alkyl, and I-substituted C1- to C4-alkyl. In the event that Ar 1 and / or Ar 2 substituted C2- to C 17-Heteroaryl is / are (including any of the aforementioned respective restricted embodiments), is / are one or more substituents independently selected from the group consisting of F, CN and F-substituted C1- to C4-alkyl.

[0167] In the event that Ar 1 and / or Ar 2 substituted C2- to C 17 -Heteroaryl is / are (including any of the aforementioned respective restricted embodiments), is / are one or more substituents independently selected from the group consisting of halogen, CN, and fully halogen-substituted C1- to C4-alkyl. In the event that Ar 1 and / or Ar 2 substituted C2- to C 17-Heteroaryl is / are (including any of the aforementioned respective restricted embodiments), is / are one or more substituents independently selected from the group consisting of F, Cl, Br, I, CN, fully F-substituted C1- to C4-alkyl, fully Cl-substituted C1- to C 12 -Alkyl, fully Br-substituted C1- to C4-alkyl, and fully I-substituted C1- to C4-alkyl. In the event that Ar 1 and / or Ar 2 substituted C2- to C 17 -Heteroaryl is / are (including any of the aforementioned respective restricted embodiments), is / are one or more substituents independently selected from the group consisting of F, CN and fully F-substituted C1- to C4-alkyl. In the event that Ar 1 and / or Ar 2 substituted C2- to C 17-Heteroaryl is / are (including any of the aforementioned respective restricted embodiments), is / are one or more substituents independently selected from the group consisting of F, CN and CF3. In the event that Ar 1 and / or Ar 2 substituted C2- to C 17 -Heteroaryl is / are (including any of the aforementioned respective restricted embodiments), is / are the one or more substituents F.

[0168] It may be provided that Ar 1 selected from groups of the following structures Ar 1 -1 to Ar 1 -5 where the respective structure is bound to *1 to M1*1.

[0169] It may be provided that Ar 2 selected from groups of the following structures Ar 2 -1 to Ar 2 -5 where the respective structure is bound to *2 to M2*2.

[0170] It may be provided that Ar 1and Ar 2 are selected the same way.

[0171] Hal 1 and Hal 2 are independently selected from halogens. Hal 1 and Hal 2 can be independently selected from the group consisting of Cl, Br and I. Hal 1 and Hal 2 Each can be Br.

[0172] M 1 and M 2 are independently selected from M'R' m .

[0173] M' is a metal. M' can be a monovalent or divalent metal. M' can be selected from the group consisting of alkali and alkaline earth metals, preferably from Li or Mg.

[0174] R' is independently selected from the group consisting of an electron donor compound, preferably an ether compound such as diethyl ether (Et2O) or tetrahydrofuran (THF), and a halogen such as Cl or Br.

[0175] The combination of formula (III) can Ar 1 Li*OEt2 or Ar1 MgHal with Hal = Cl or Br.

[0176] The combination of formula (IV) can Ar 2 Li*OEt2 or Ar 2 MgHal with Hal = Cl or Br.

[0177] M 3 is a metal. M 3 It can be a divalent, trivalent, or tetravalent metal. M 3 It can be selected from the group consisting of main group metals or transition metals, such as Sn or Zn.

[0178] R'' is independently a hydrocarbyl group. R'' can be an alkyl group, an aryl group, an alkenyl group, or an alkynyl group. R'' can be an alkyl group, such as a C1 to C 12 -Alkyl group, a C1 to C 10 -Alkyl group, a C1 to C8 alkyl group, a C1 to C6 alkyl group, a C1 to C4 alkyl group, a C1 to C3 alkyl group, a C1 to C2 alkyl group, most preferably methyl.

[0179] The combination of formula (V) can Ar 1 -Zn-Ar 2 or (Ar1 )(Ar 2 )Sn(CH3)2 be.

[0180] According to one aspect of the invention, the method according to the invention comprises a step of reacting a compound of formula (II) with a compound of formula (V) Ar 1 -M 3 -Ar 2 (V), preferably with (Ar 1 )(Ar 2 )Sn(CH3)2 to obtain the combination of formula (I)

[0181] The reaction step can be carried out in a solvent, such as an organic solvent. The organic solvent can be selected from nonpolar solvents, such as organic hydrocarbons like toluene, benzene, xylene, etc., or from polar solvents, such as ethers like Et₂O.

[0182] The reaction step can be carried out in the presence of a base, such as an organic base like butyllithium. Details and definitions of the invention

[0183] An organic compound, as defined herein, is generally any chemical compound containing carbon (with the exception of some compounds generally referred to as inorganic, such as carbonates, cyanides, carbon dioxide, diamond, etc.). The term organic compound used herein also includes compounds such as organometallic compounds, for example, metallocenes, etc.

[0184] Unless explicitly stated otherwise, all compounds, groups, units, substituents, etc. shown herein, in particular by structural formulas, by systematic names, etc., include their respective partially and fully deuterated derivatives.

[0185] The term "zero-valent," as used herein, refers to a metal in the oxidation state o, that is, specifically metals from which no electron has been removed. The zero-valent metal can exist in the form of zero-valent atoms, pure metal, alloys, etc.

[0186] The term “trivalent”, as used herein, refers to a nitrogen atom with a single bond and a double bond and contains a single pair of electrons.

[0187] The term “hydrocarbyl group”, as used herein, is to be understood as encompassing any organic group comprising carbon atoms, in particular organic groups such as alkyl, aryl, heteroaryl, heteroalkyl, especially those groups which are substituents commonly used in organic electronics.

[0188] The term ‘conjugated system’, as used herein, refers to a system of alternating π and σ bonds, or a molecule with alternating single and multiple bonds, i.e., double bonds, or a system with one or more diatomic structural units in which the π bond between its atoms may be replaced by an atom carrying at least a single pair of electrons, typically a divalent O or S atom.

[0189] The term "alkyl," as used herein, is intended to encompass linear, branched, and cyclic alkyl. For example, C3 alkyl may be selected from n-propyl and isopropyl. Similarly, C4 alkyl includes n-butyl, sec-butyl, and t-butyl. Likewise, C6 alkyl includes n-hexyl and cyclohexyl.

[0190] The subscript n in C n refers to the total number of carbon atoms in the respective alkyl, arylene, heteroarylene or aryl group.

[0191] The term "aryl" or "arylene," as used herein, is intended to include phenyl (C6-aryl), condensed aromatics such as naphthalene, anthracene, phenanthrene, tetracene, etc. It also includes biphenyl and oligo- or polyphenyls such as terphenyl, phenyl-substituted biphenyl, phenyl-substituted terphenyl (such as tetraphenylbenzene groups), etc. "Arylene" or "heteroarylene" refers to groups to which two other substituents are bonded. In the present description, the term "aryl group" or "arylene group" may refer to a group comprising at least one aromatic hydrocarbon substituent, and all elements of the aromatic hydrocarbon substituent may have p-orbitals forming a conjugation, for example, a phenyl group, a naphthyl group, an anthracene group, a phenanthrene group, a pyrinyl group, a fluorenyl group, and the like.Spiro compounds, in which two aromatic residues are linked via a spiro atom, such as 9,9'-spirobi[9H-fluoren]yl, are also included. The aryl or arylene group can comprise a monocyclic or condensed polycyclic (i.e., linkages sharing adjacent pairs of carbon atoms) functional group.

[0192] The term “heteroaryl,” as used herein, refers to aryl groups in which at least one carbon atom is substituted with a heteroatom. The term “heteroaryl” can refer to aromatic heterocycles with at least one heteroatom, and all elements of the heteroaromatic hydrocarbon residue may have p-orbitals forming a conjugation. The heteroatom may be selected from N, O, S, B, Si, P, Se, preferably from N, O, and S. A heteroarylene ring may comprise at least one to three heteroatoms. Preferably, a heteroarylene ring may comprise at least one to three heteroatoms individually selected from N, S, and / or O. Just as in the case of “aryl” / “arylene,” the term “heteroaryl” includes, for example, spiro compounds in which two aromatic residues are linked together, such as spiro[fluorene-9,9'-xanthene].Other examples of heteroaryl groups are diazine, triazine, dibenzofuran, dibenzothiofuran, acridine, benzoacridine, dibenzoacridine, etc.

[0193] The subscript n in C n -Heteroaryl refers solely to the number of carbon atoms, excluding the number of heteroatoms. In this context, it is clear that a C3 heteroaryl group is an aromatic compound comprising three carbon atoms, such as pyrazole, imidazole, oxazole, thiazole, and the like.

[0194] The term "halogenated" refers to an organic compound in which one hydrogen atom has been replaced by a halogen atom. The term "perhalogenated" refers to an organic compound in which all hydrogen atoms have been replaced by halogen atoms. The meaning of the terms "fluorinated" and "perfluorinated" is analogous.

[0195] The term “alkenyl”, as used herein, refers to a group of -CR 1 =CR 2 R 3 , which includes a carbon-carbon double bond.

[0196] The term “perhalogenated”, as used herein, refers to a hydrocarbyl group in which all hydrogen atoms of the hydrocarbyl group are replaced by halogen atoms (F, Cl, Br, I).

[0197] The term ‘alkoxy’, as used herein, refers to a structural fragment of the formula -OR, where R is hydrocarbyl, preferably alkyl or cycloalkyl.

[0198] The term ‘thioalkyl’, as used herein, refers to a structural fragment of the formula -SR, where R is hydrocarbyl, preferably alkyl or cycloalkyl.

[0199] In the present description, the term single bond refers to a direct bond.

[0200] For the purposes of the invention, a group is ‘substituted’ with another group if one of the hydrogen atoms included in that group is replaced by another group, wherein the other group is the substituent.

[0201] According to the present disclosure in a formula showing the following bonding situation, the group A can be bonded to any suitable bonding position. In a situation where the bond of A crosses more than one ring, the group A can be bonded to any suitable bonding position of each ring that is crossed by the bond.

[0202] For the purposes of the invention, the term "between" in relation to a layer that is between two other layers does not preclude the presence of further layers that may be arranged between that layer and either of the other two layers. For the purposes of the invention, the term "in direct contact" in relation to two layers that are in direct contact with each other means that no further layer is arranged between these two layers. A layer deposited on the top surface of another layer is considered to be in direct contact with that layer.

[0203] In the context of this description, the term "essentially 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 approximately ≥ 380 nm to approximately ≤ 780 nm.

[0204] With regard to the organic light-emitting device according to the invention, the compounds mentioned in the experimental part may be most preferred.

[0205] The organic electroluminescent device (OLED) can be a bottom- or top-emission device.

[0206] Another aspect is directed at 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.

[0207] In the present invention, the following defined terms shall apply, these definitions unless a different definition is given in the claims or elsewhere in this description.

[0208] In the context of the present description, the term “different” or “differs” in connection with the matrix material means that the matrix material differs in its structural formula.

[0209] 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).

[0210] The terms "OLED" and "organic light-emitting diode" are used interchangeably and have the same meaning. The term "organic electroluminescent device," as used here, can encompass both organic light-emitting diodes and organic light-emitting transistors (OLETs).

[0211] As used herein, “weight percent”, “wt%”, wt%, “weight percent”, “wt%”, 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 that component, substance, or agent of the respective electron transport layer 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 such that it does not exceed 100 wt%.

[0212] As used herein, “volumetric percent”, “vol%”, “volumetric percent”, “vol%”, 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 that electron transport layer thereof, 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 vol%.

[0213] All numerical values ​​herein are assumed to be modified by the term "approximately," whether explicitly stated or not. As used here, the term "approximately" refers to a variation of the numerical set that may occur. Whether modified by the term "approximately" or not, the claims include equivalents to the sets.

[0214] It should be noted that, as used in this description and the attached claims, the singular forms “ein”, “eine” and “der” include plural references unless the content clearly specifies otherwise.

[0215] The terms "free from", "do not contain", and "do not include" do not exclude impurities. Impurities have no technical effect with regard to the problem solved by the present invention. The term "free from" a compound means that such a compound / material is not intentionally added to the layer during processing.

[0216] Preferably, the semiconductor layer comprising the compound of formula (I) is substantially non-emissive or non-emitting.

[0217] The operating voltage, also known as U, is measured in volts (V) at 10 milliamperes per square centimeter (mA / cm2).

[0218] Efficiency in candela per ampere, also known as cd / A, is measured in candela per ampere at 10 milliamperes per square centimeter (mA / cm2).

[0219] External quantum efficiency, also known as EQE, is measured in percent (%).

[0220] The color space is described by the CIE x and CIE y coordinates (International Commission on Illumination 1931). CIE y is particularly important for blue emission. A smaller CIE y value indicates a deeper blue color. Efficiency values ​​are compared at the same CIE y value.

[0221] 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).

[0222] The terms “OLED”, “organic light-emitting diode”, “organic light-emitting device”, “organic optoelectronic device” and “organic light-emitting diode” are used simultaneously and have the same meaning.

[0223] The terms “Lebensdauer” and “Lebensdauer” are used simultaneously and have the same meaning.

[0224] The anode and cathode can be described as anode electrode / cathode electrode or anode electrode / cathode electrode or anode electrode layer / cathode electrode layer.

[0225] The room temperature, also known as ambient temperature, is 23 °C.

[0226] The embodiments are illustrated in more detail below with reference to examples. The exemplary aspects are discussed in detail. DESCRIPTION OF THE DRAWINGS

[0227] The aforementioned components, as well as the claimed components and the components to be used in the described embodiments according to the invention, are not subject to any special exceptions with regard to their size, shape, material selection and technical concept, so that the selection criteria known in the relevant field can be applied without restrictions.

[0228] Additional details, features, and advantages of the invention are disclosed in the dependent claims and the following description of the respective figures, which illustrate preferred embodiments according to the invention. However, each embodiment does not necessarily represent the full scope of the invention, and reference is therefore made to the claims and herein to interpret the scope of the invention. It is understood that both the foregoing general description and the following detailed description are merely exemplary and explanatory and are intended to provide a further explanation of the present invention as claimed. Fig. Figure 1 is a schematic sectional view of an organic light-emitting diode (OLED) according to an exemplary embodiment of the present invention; Fig.Figure 2 is a schematic sectional view of an OLED according to an exemplary embodiment of the present invention. Fig. Figure 3 is a schematic sectional view of a tandem OLED comprising a charge generation layer, according to an exemplary embodiment of the present invention. FORM OF EXECUTION OF THE DEVICE ACCORDING TO THE INVENTION

[0229] The exemplary embodiments of the present invention will now be discussed in detail, examples of which are illustrated in the accompanying drawings, where identical reference numerals consistently refer to identical elements. The exemplary embodiments are described below in order to explain the aspects of the present invention with reference to the figures.

[0230] Where a first element is described herein as being formed or arranged "on" a second element, the first element may be placed directly on top of the second element, or one or more other elements may be placed between them. Where a first element is described as being formed or arranged "directly on" a second element, no other elements are placed between them.

[0231] Fig.Figure 1 is a schematic sectional view of an organic light-emitting diode (OLED) 100 according to an exemplary embodiment of the present invention. The OLED 100 comprises 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 formed directly on the EML 150. An electron injection layer (EIL) 180 is arranged on the electron transport layer (ETL) 160. The cathode 190 is arranged directly on the electron injection layer (EIL) 180.

[0232] Instead of a single electron transport layer 160, an electron transport layer (ETL) can optionally be used.

[0233] Fig. Figure 2 is a schematic sectional view of an OLED 100 according to a further exemplary embodiment of the present invention. Fig. 2 differs from Fig.1 in that the OLED 100 of Fig. 2 comprises an electron blocking layer (EBL) 145 and a hole blocking layer (HBL) 155.

[0234] With reference to Fig. 2 the OLED 100 comprises 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.

[0235] Fig. Figure 3 is a schematic sectional view of a tandem OLED 200 according to a further exemplary embodiment of the present invention. Fig. 3 differs from Fig. 2 in that the OLED 100 of Fig. 3 further comprises a charge generation layer and a second emission layer.

[0236] With reference to Fig.3 The OLED 200 comprises 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 emission 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 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, and a second electron injection layer. (EIL) 181 and a cathode 190.

[0237] Although in Fig. 1, Fig. 2 and Fig.Not shown in Figure 3, a sealing layer can also be formed on the cathode electrodes 190 to seal the OLEDs 100 and 200. Various other modifications can also be applied.

[0238] In the following, one or more exemplary embodiments of the present invention are described in detail with reference to the following examples. However, these examples are not intended to limit the purpose and scope of the claims to one or more exemplary embodiments of the present invention. experimental part Synthesis procedure Synthesis of Bis(4-cyano-2,3,5,6-tetrafluorophenyl)dimethylstannan

[0239] i-PrMgCl (2.0 M in Et₂O, 1.9 mL, 3.8 mmol) was dissolved in dry Et₂O (8 mL) and cooled to -78 °C. After dropwise addition of a solution of 4-bromo-2,3,5,6-tetrafluorobenzonitrile (1.000 g, 3.937 mmol) in dry Et₂O, the reaction mixture was stirred for 4 h. Dichlorodimethylstannane (0.411 g, 1.87 mmol) was added as a solid, and the mixture was gradually warmed to room temperature overnight. After removal of all volatile components under reduced pressure, the residue was reconstituted in dry C₆H₆ (20 mL) and filtered through a Schlenk frit. Removal of all volatile components from the filtrate under reduced pressure yielded dimethylbis(4-cyano-2,3,5,6-tetrafluorophenyl)stannan as a colorless solid. Yield: 0.290 g (0.584 mmol, 31%).

[0240] 1 H NMR (300.0, CDC13): δ = 0.58 (s, 6H) ppm.

[0241] 19 F NMR (282.3 MHz, CDCl3): δ = -(119.9-120.3) (m, 4F), -(131.1-131.3) (m, 4F) ppm. Synthesis of 2,3,6,7-tetrafluoro-9,10-bis(4-cyano-2,3,5,6-tetrafluorophenyl)-9,10-dihydro-9,10-diboraanthracene (E2)

[0242] A thick-walled glass ampoule was filled with 2,3,6,7-tetrafluoro-9,10-dibromo-9,10-dihydro-9,10-diboraanthracene (0.100 g, 0.247 mmol), bis(4-cyano-2,3,5,6-tetrafluorophenyl)dimethylstannan (0.123 g, 0.248 mmol), and dry C6H6 (4 ml). The ampoule was flame-sealed under vacuum and then heated in an oven at 180 °C for 3 days. After cooling to room temperature, the ampoule was opened and the liquid was separated from the solid using a syringe. Washing the solid with dry C6H6 (3 x 1.2 ml) gave the product 2,3,6,7-tetrafluoro-9,10-bis(4-cyano-2,3,5,6-tetrafluorophenyl)-9,10-dihydro-9,10-diboraanthracene as beige crystals. Yield: 0.104 g (0.175 mmol, 71%).

[0243] The solubility of 2,3,6,7-tetrafluoro-9,10-bis(4-cyano-2,3,5,6-tetrafluorophenyl)-9,10-dihydro-9,10-diboraanthracene in all common solvents is too low to record NMR spectra. Synthesis of 2,3,6,7-Tetrafluoro-9,10-bis(perfluoropyridin-4-yl)-9,10-dihydro-9,10-diboraanthracene (E1)

[0244] A thick-walled glass ampoule was filled with 2,3,6,7-tetrafluoro-9,10-dibromo-9,10-dihydro-9,10-diboraanthracene (0.500 g, 1.23 mmol), dimethylbis(perfluoropyridin-4-yl)stannan (0.556 g, 1.24 mmol), and dry C6H6 (10 ml). The ampoule was flame-sealed under vacuum and then heated in an oven at 180 °C for 90 h. After cooling to room temperature, the ampoule was opened and the liquid was separated from the solid using a syringe. Washing the solid with dry C6H6 (4 × 1 ml) gave the product 2,3,6,7-tetrafluoro-9,10-bis(perfluoropyridin-4-yl)-9,10-dihydro-9,10-diboraanthracene as yellow crystals. Yield: 0.580 g (1.06 mmol, 86%).

[0245] 1 H NMR (300.0, CDCl3): δ = 7.47-7.39 (m, 4H) ppm.

[0246] 19 F NMR (282.3 MHz, CDCl3): δ = -(89.5-89.8) (m, 4F), -(124.2-124.4) (m, 4F), -(131.9-132.3) (m, 4F) ppm. Synthesis of 2,3,6,7-Tetrafluoro-9,10-bis(2,4,6-tris(trifluoromethyl)phenyl)-9,10-dihydro-9,10-diboraanthracene (E7)

[0247] 2-Iodo-1,3,5-tris(trifluoromethyl)benzene (0.204 g, 0.500 mmol) was dissolved in dry Et₂O (8 mL) and cooled to -78 °C. After the dropwise addition of n-BuLi (2.37 M in n-hexane, 0.21 mL, 0.50 mmol), the mixture was stirred for 4 h. 2,3,6,7-Tetrafluoro-9,10-dibromo-9,10-dihydro-9,10-diboraanthracene (0.050 g, 0.12 mmol) was dissolved in dry toluene (4 mL) and added dropwise to the reaction mixture. The mixture was gradually warmed to room temperature overnight and slaked by the addition of H₂O (10 mL). The two phases were separated, and the aqueous phase was extracted with CHCl₃ (2 × 10 mL). The combined organic phases were washed with saturated aqueous NaCl solution (10 ml), dried over MgSO4, filtered, and the filtrate was evaporated to dryness under reduced pressure.Column chromatography (silica gel, cyclohexane:CHCl3 = 10:1) yielded 2,3,6,7-tetrafluoro-9,10-bis(2,4,6-tris(trifluoromethyl)phenyl)-9,10-dihydro-9,10-diboraanthracene as a colorless solid. Yield: 0.018 g (0.022 mmol, 18%).

[0248] 1 H NMR (250.1 MHz, CDCl3): δ = 8.25 (s, 4H), 7.05-6.96 (m, 4H) ppm. [1] AS Filatov, EA Jackson, LT Scott, MA Petrukhina, Angew. Chemistry - International Ed. 2009, 48, 8473-8476. [2] S. Brend'amour, J. Gilmer, M. Bolte, HW Lerner, M. Wagner, Chem. - A Eur. J. 2018, 16910-16918. Supporting materials

[0249] LiQ is lithium 8-hydroxyquinolinolate, CAS 850918-68-2

[0250] H09 is an emitter host and BD200 is a blue fluorescent emitter dopant, both commercially available from SFC, Korea. Standard procedure

[0251] OLEDs are driven by constant current circuits. These circuits can supply a constant current over a given voltage range. The wider the voltage range, the greater the power losses of such devices. Therefore, the change in the drive voltage during operation must be minimized.

[0252] The drive 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 drive operation.

[0253] Voltage stability is measured by determining the difference in the drive voltage after 50 hours and after 1 hour of drive operation at a constant current density. Here, a current density of 30 mA / cm² is used. 2 used. Measurements are taken at room temperature. dU[V]=U(50 h,30 mA / cm2)−U(1 h,30 mA / cm2) Apparatus experiments

[0254] The structure of a blue OLED model in which the performance of the compounds according to the invention was investigated is shown in Table 1a. Table 1a layer material Concentration [vol%] Layer thickness [nm] anode ITO / Ag / ITO 100 / 100 / 100 10 / 120 / 10 HIL F1:p dopant different 10 HTL F1 100 121 EBL F2 100 5 EML H09: BD200 97:3 20 HBL F3 100 5 ETL F4:LiQ 50:50 31 Urgent Yb 100 2 cathode Ag:Mg 90:10 13 Top layer F1 100 75 ITO is indium tin oxide.

[0255] The results are given in Table 1b. Table 1b HIL p-doper CIEy Voltage 10mA / cm 2 [V] Ceff / CIEy10mA / cm 2 [cd / A] LT9730mA / cm 2 [h] dU30mA / cm 2 (1-50h)[V] E1, 10 wt. % 0.046 3.78 150 102 0.003 E1, 20 wt. % 0.046 3.73 149 88 0.003

[0256] The results showed that the inventive compound E1 is completely on par with prior art p-doping materials in terms of operating voltage, current efficiency and device lifetime, and additionally enables excellent voltage stability.

[0257] A direct comparison of the compounds according to the invention with prior art triarylboranes such as tris(pentafluorophenyl)borane (BF15) was not possible, as BF15 was found to be too volatile to be approved for use in the prior art thermal vacuum evaporation tool used for device manufacture.

[0258] The features disclosed in the foregoing description and in the dependent claims can be essential, both separately and in any combination thereof, for realizing the aspects of the disclosure listed in the independent claims in various forms thereof.

Claims

[1] An organic electronic device (100) comprising an anode layer (120), a cathode layer (190), an emission layer (150) and a semiconductor layer, comprising a first compound, wherein the first compound has the formula (I), wherein - R 1 up to R4 are independently selected from the group consisting of F, halogen-substituted C1 to C 12 -Alkyl and H, wherein at least two of R 1 to R 4 are selected from F and halogen-substituted C1 to C 12 -Alkyl; - R 1' to R 4' are independently selected from the group consisting of F, halogen-substituted C1- to C 12 -Alkyl and H, wherein at least two of R 1' to R 4' are selected from F and halogen-substituted C1 to C 12 -Alkyl; - Ar 1 and Ar 2 are independently selected from the group consisting of substituted C6-bis C18 -Aryl, unsubstituted C2- to C 17 -Heteroaryl and substituted C2-bisC 17 -Heteroaryl; - the substituted C6 to C 18 -Aryl is substituted with at least one substituent independently selected from the group consisting of halogen, CN and halogen-substituted C1- to C 12 -Alkyl; and - the substituted C2- to C 17 -Heteroaryl is substituted with at least one substituent independently selected from the group consisting of halogen, CN and halogen-substituted C1- to C 12 -Alkyl. [2] The organic electronic device (100) according to claim 1, wherein - R 1 to R 4 and R 1' to R 4' F are; or - R 1 to R 3 and R 2' to R 4' F are and R 4 and R 1' H are; or - R 2 , R3 , R 2' and R 3' F are and R 1 ; R 4 , R 1' and R 4' H are. [3] The organic electronic device (100) according to any one of the preceding claims, wherein - at least one of Ar 1 and Ar 2 independently selected from the group consisting of substituted C6 to C 18 -Aryl; and - the substituted C6 to C 18 -Aryl is substituted with at least one substituent independently selected from the group consisting of halogen, CN and halogen-substituted C1- to C 12 -Alkyl, wherein at least one of the substituents is selected from the group consisting of CN and halogen-substituted C1- to C 12 -Alkyl. [4] The organic electronic device (100) according to claim 1 or 2, wherein Ar 1 and Ar 2They are independently selected from the group consisting of substituted phenyl and substituted pyridyl. [5] The organic electronic device (100) according to any one of the preceding claims, wherein - the substituted C6 to C 18 -Aryl is substituted with at least one substituent independently selected from the group consisting of F, CN and F-substituted C1- to C4-alkyl; and - the substituted C2- to C 17 -Heteroaryl is substituted with at least one substituent which is independently selected from the group consisting of F, CN and F-substituted C1- to C4-alkyl. [6] The organic electronic device (100) according to claim 5, wherein the F-substituted C1- to C4-alkyl is trifluoromethyl. [7] The organic electronic device (100) according to any one of the preceding claims, wherein the first compound is selected from E1 to E10 [8] The organic electronic device (100) according to any of the preceding claims, wherein the semiconductor layer comprising the first compound is a hole transport layer (140), a hole injection layer (130) or a hole generation layer. [9] The organic electronic device (100) according to claim 8, wherein the semiconductor layer further comprises a hole transport matrix interconnect. [10] The organic electronic device (100) according to claim 8, wherein the semiconductor layer consists of the first compound. [11] The organic electronic device (100) according to any of the preceding claims, wherein the organic electronic device is an organic light-emitting diode (100). [12] A display device comprising at least one organic light-emitting diode (100) according to claim 11. [13] A compound with formula (Ib) where - R 1 to R 4are independently selected from the group consisting of F, halogen-substituted C1 to C 12 -Alkyl and H, wherein at least two of R 1 to R 4 are selected from F and halogen-substituted C1 to C 12 -Alkyl; - R 1' to R 4' are independently selected from the group consisting of F, halogen-substituted C1- to C 12 -Alkyl and H, wherein at least two of R 1' to R 4' are selected from F and halogen-substituted C1 to C 12 -Alkyl; - Ar 1 and Ar 2 are independently selected from the group consisting of substituted C6 to C 18 -Aryl, unsubstituted C2- to C 17 -Heteroaryl and substituted C2- to C 17 -Heteroaryl; - the substituted C6 to C 18-Aryl is substituted with at least one substituent independently selected from the group consisting of halogen, CN and halogen-substituted C1- to C 12 -Alkyl, wherein at least one of the substituents of the substituted C6- to C 18 -Aryls is selected from the group consisting of CN and halogen-substituted C1- to C 12 -Alkyl; and - the substituted C2- to C 17 -Heteroaryl is substituted with at least one substituent independently selected from the group consisting of halogen, CN and halogen-substituted C1- to C 12 -Alkyl. [14] Use of a compound having formula (I) as defined in any one of claims 1 to 11 or of a compound according to claim 13 as a p-doper in an organic semiconductor material or in a hole injection layer (130). [15] A method for producing a compound having formula (Ib) according to claim 13, wherein the method comprises a step: the reaction of a compound of formula (II) with a compound of formula (III) and with a compound of formula (IV) M 1 -Ar 1 (III) M 2 - Ar 2 (IV), or with a combination of the formula (V) Ar 1 -M 3 -Ar 2 (V), to obtain the connection of formula (Ib) where - R 1 to R 4 are independently selected from the group consisting of F, halogen-substituted C1- to C 12 -Alkyl and H, wherein at least two of R1 to R4 are selected from F and halogen-substituted C1- to C 12 -Alkyl; - R 1' to R 4'are independently selected from the group consisting of F, halogen-substituted C1- to C 12 -Alkyl and H, wherein at least two of R 1' to R 4' are selected from F and halogen-substituted C1 to C 12 -Alkyl; - Ar 1 and Ar 2 are independently selected from the group consisting of substituted C6 to C 18 -Aryl, unsubstituted C2- to C 17 -Heteroaryl and substituted C2- to C 17 -Heteroaryl; - the substituted C6 to C 18 -Aryl is substituted with at least one substituent independently selected from the group consisting of halogen, CN and halogen-substituted C1- to C 12 -Alkyl, wherein at least one of the substituents of the substituted C6- to C 18 -Aryls is selected from the group consisting of CN and halogen-substituted C1- to C 12 -Alkyl; - the substituted C2- to C 17-Heteroaryl is substituted with at least one substituent independently selected from the group consisting of halogen, CN and halogen-substituted C1- to C 12 -Alkyl; - Hal 1 and Hal 2 are independently selected from halogen; - M 1 and M 2 independently selected from M'R' m ; where M' is a metal and R' is independently selected from the group consisting of an electron-donating compound and a halogen, where m is an integer from 0 to 2; - M 3 independently selected from M''R'' n , where M'' is a metal and R'' is independently a hydrocarbyl group, where n is an integer from 0 to 2.

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