ORGANIC ELECTRONIC DEVICE AND DISPLAY DEVICE COMPRISING COMPOUNDS OF Formula (I) AND COMPOUNDS OF Formula (Ia)

Abstract

The present invention relates to an organic electroluminescent device comprising a compound of formula (I) and a compound of formula (Ia).

Description

Technical Field

[0001] The present invention relates to an organic electronic device and a display device including a compound of formula (I) and a compound of formula (Ia). Background Art

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

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

[0004] The performance of an organic light emitting diode can be affected by the characteristics of the semiconductor layer, and in particular, can be affected by the characteristics of the compound of formula (I) also included in the semiconductor layer.

[0005] There is still a need to improve the performance and stability of organic semiconductor materials, semiconductor layers, and their organic electronic devices, particularly to achieve improved brightness, longer lifespan, improved efficiency such as current efficiency and external quantum efficiency, and / or voltage stability over time. The organic compounds of the present invention exhibit a significant energy gap (E-Gap), which is the difference between the HOMO level and the LUMO level, and thus the compounds exhibit very low absorption in the visible light wavelength range.

[0006] In addition, the compounds exhibit good volatility and thermal stability for fabricating OLED devices well. Summary of the Invention

[0007] One aspect of the present invention provides an organic electroluminescent device including an anode layer, a cathode layer, a first light emitting layer, a second light emitting layer, and a charge generation layer,

[0008] wherein the charge generation layer is disposed between the first light emitting layer and the second light emitting layer;

[0009] wherein the charge generation layer includes an n-type charge generation layer and a p-type charge generation layer;

[0010] wherein the n-type charge generation layer is closer to the anode layer than the p-type charge generation layer;

[0011] wherein the p-type charge generation layer contains the compound of formula (I)

[0012]

[0013] wherein in formula (I), A is selected from formula (II)

[0014]

[0015] wherein R 1 to R 5 are independently selected from H, D, CN, CF3, partially or fully perfluorinated C1-C8 alkyl groups,

[0016] R 1 or R 5 at least one of which is selected from CN, CF3, partially or fully perfluorinated C1-C8 alkyl groups,

[0017] R 1 to R 5 at least three of which are selected from CN, CF3, partially or fully perfluorinated C1-C8 alkyl groups,

[0018] wherein "*" represents the bonding position;

[0019] and wherein A is not selected from:

[0020]

[0021]

[0022] According to a preferred embodiment, A does not include:

[0023]

[0024] According to a preferred embodiment, A does not include:

[0025]

[0026] Another aspect of the present invention provides a compound of formula (Ia)

[0027]

[0028] wherein in formula (Ia), A 1 is selected from the group of formula (IIa)

[0029]

[0030] wherein

[0031] R 1to R 5 independently selected from H, D, CN, CF3 or a partially or fully perfluorinated C1-C8 alkyl group,

[0032] R 1 or at least one of R 5 is selected from CN, CF3 or a partially or fully perfluorinated C1-C8 alkyl group,

[0033] R 1 to R 5 at least three of which are selected from CN, CF3 or a partially or fully perfluorinated C1-C8 alkyl group,

[0034] R 1 to R 5 at least one of which is selected from CN, and

[0035] R 1 to R 5 at least one of which is selected from CF3 or a partially or fully perfluorinated C1-C8 alkyl group,

[0036] wherein "*" represents the bonding position;

[0037] wherein for A 1 , the following parts are excluded:

[0038]

[0039]

[0040] According to a preferred embodiment, for A 1 , the following parts are excluded:

[0041]

[0042] It should be noted that unless otherwise noted, throughout the application and the claims, any A n , Ar n , B n , R n etc. always refer to the same part.

[0043] In this specification, when no definition is provided otherwise, "substituted" means substituted with deuterium, C1-C 12 alkyl and C1-C 12 alkoxy.

[0044] However, in this specification, "aryl-substituted" means substituted with one or more aryl groups, which aryl groups themselves may be substituted with one or more aryl and / or heteroaryl groups.

[0045] Accordingly, in this specification, "heteroaryl-substituted" means substituted by one or more heteroaryl groups, which heteroaryl groups themselves may be substituted by one or more aryl and / or heteroaryl groups.

[0046] In this specification, when no definition is provided otherwise, "alkyl group" means a saturated aliphatic hydrocarbon group. The alkyl group can be C1 to C 12 alkyl group. More specifically, the alkyl group can be C1 to C 10 alkyl group or C1 to C6 alkyl group. For example, a C1 to C4 alkyl group contains 1 to 4 carbons in the alkyl chain and can be selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl.

[0047] Specific examples of the alkyl group can be methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group.

[0048] The term "cycloalkyl" means a saturated hydrocarbon group derived by formally removing a hydrogen atom from a ring atom contained in the corresponding cycloalkane. Examples of the cycloalkyl group can be cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, methylcyclohexyl group, adamantyl group, etc.

[0049] The term "hetero" is understood to mean that at least one carbon atom in a structure that can be formed by covalently bonded carbon atoms is replaced by another polyvalent atom. Preferably, the heteroatom is selected from B, Si, N, P, O, S; more preferably from N, P, O, S.

[0050] In this specification, "aryl group" means a hydrocarbon group generated by formally removing a hydrogen atom from an aromatic ring in the corresponding aromatic hydrocarbon. An aromatic hydrocarbon means a hydrocarbon containing at least one aromatic ring or aromatic ring system. An aromatic ring or aromatic ring system means a planar ring or ring system of covalently bonded carbon atoms, wherein the planar ring or ring system contains a conjugated system of delocalized electrons that satisfies the Hückel rule. Examples of the aryl group include: monocyclic groups such as phenyl or tolyl; polycyclic groups containing multiple aromatic rings connected by single bonds such as biphenyl; and polycyclic groups containing fused rings such as naphthyl or fluoren-2-yl.

[0051] Similarly, heteroaryl is particularly preferably understood as a group derived by formally removing a ring hydrogen from a heteroaromatic ring in a compound containing at least one heteroaromatic ring.

[0052] Heterocycloalkyl is particularly preferably understood as a group derived by formally removing a ring hydrogen from a saturated cycloalkyl ring in a compound containing at least one saturated cycloalkyl ring.

[0053] The term "fused aryl ring" or "condensed aryl ring" is understood to mean that when two aryl rings share at least two common sp 2 hybridized carbon atoms, they are considered to be fused or condensed.

[0054] The term "electron-withdrawing group" refers to a chemical group in a molecule that can draw electrons away from an adjacent part of the molecule. The distance over which an electron-withdrawing group can exert its effect, i.e., the number of bonds across which the electron-withdrawing effect extends, is increased through a conjugated π-electron system such as an aromatic system. Examples of electron-withdrawing groups include NO2, CN, halogen, Cl, F, partially fluorinated or perfluorinated alkyl groups, and partially fluorinated or perfluorinated C 12 alkyl groups, partially fluorinated or perfluorinated alkoxy groups, and partially fluorinated or perfluorinated C1 to C6 alkoxy groups.

[0055] In this specification, a single bond means a direct bond.

[0056] The term "n-type charge generation layer" is sometimes also referred to as n-CGL or electron generation layer in the art and is intended to include both.

[0057] The term "p-type charge generation layer" is sometimes also referred to as p-CGL or hole generation layer in the art and is intended to include both.

[0058] The terms "without", "free of", "not containing" do not exclude impurities that may be present in the compound before deposition. The impurities have no technical effect on the object achieved by the present invention.

[0059] The term "contact sandwich" refers to a three-layer arrangement in which an intermediate layer is in direct contact with two adjacent layers.

[0060] The terms "light-absorbing layer" and "photoabsorbing layer" are used synonymously.

[0061] The terms "light-emitting layer", "layer that emits light", and "light-emitting layer" are used synonymously.

[0062] The terms "OLED", "organic light-emitting diode", and "organic light-emitting device" are used synonymously.

[0063] The terms "anode", "anode layer", and "anode electrode" are used synonymously.

[0064] The terms "cathode", "cathode layer", and "cathode electrode" are used synonymously.

[0065] In this specification, hole characteristics refer to the ability, when an electric field is applied, to supply electrons to form holes and for the holes formed in the anode due to the conductive characteristics according to the highest occupied molecular orbital (HOMO) energy level to be easily injected into the light-emitting layer and transported in the light-emitting layer.

[0066] In addition, the electronic property refers to the ability to accept electrons when an electric field is applied and for the electrons formed in the cathode due to the conductive property according to the lowest unoccupied molecular orbital (LUMO) energy level to be easily injected into and transported in the light-emitting layer.

[0067] Advantageous Effects

[0068] Surprisingly, it has been found that the organic electroluminescent device and the compound according to the present invention solve the fundamental problems of the present invention by making the device superior to the organic electronic devices known in the prior art in various aspects, particularly superior to the organic electronic devices known in the prior art in terms of improved brightness, longer lifespan, improved efficiency such as current efficiency and external quantum efficiency, improved voltage and / or stability over time. The organic compounds of the present invention exhibit a remarkable energy gap (E-Gap), which is the difference between the HOMO energy level and the LUMO energy level, and thus the compounds exhibit very low absorption in the visible light wavelength range. Low absorption results in a reduction in external quantum efficiency, current density, and / or luminous flux.

[0069] In addition, the compounds exhibit suitable volatility and thermal stability for the good manufacture of OLED devices.

[0070] Electroluminescent devices such as OLEDs must not only match the color purity and long-term stability of competing technologies, but they must also offer significant advantages in terms of efficiency, especially in low-power, portable applications.

[0071] A major component of the power efficiency of an OLED is the external quantum efficiency (EQE), which is defined as EQE = extracted photons / injected electrons. The power efficiency is the ratio of the optical power output as detected by the human eye to the input electrical power.

[0072] EQE is proportionally related to the luminous flux.

[0073] The luminous flux (given in lumens, lm) is defined as the amount of light that can sensitize the human eye per unit time, or the total photometric power emitted from a light source in all directions. It is normalized using the maximum sensitivity of the (ideal) eye at 555 nm (or 1 / 680 W).

[0074] The luminous intensity (measured in candela, cd) takes into account the color and direction of the light. It is the luminous flux emitted into a specific solid angle.

[0075] The brightness L is the luminous intensity, both per unit area. In applications, the typical brightness level of a mobile display is between 100 cd / m 2 and 400 cd / m 2 while for general lighting, a higher value of approximately 5000 cd / m 2 is required.

[0076] The current efficiency can be calculated as the amount of current flowing through a device having a light-emitting region necessary to produce a certain luminance L, which is expressed in cd / A.

[0077] The main limitations on the quantum efficiency and current efficiency of OLEDs are the light output coupling rate. The output coupling rate is limited by absorption losses and the guiding of electroluminescence within the device and its substrate, i.e., using less absorbing material and transparent contacts increases the output coupling rate, thus improving the external quantum efficiency, luminous flux, and current efficiency of OLEDs.

[0078] It can be shown that the compounds of the present invention exhibit a significantly high energy gap and also exhibit low absorption in the visible light wavelength range.

[0079] According to one embodiment, in formula (II), R 1 to R 5 at least one of which is selected from CN.

[0080] According to one embodiment, in formula (II), R 1 to R 5 at least one of which is selected from CF3 or a partially or fully perfluorinated C1 to C8 alkyl group.

[0081] According to one embodiment, in formula (II) and / or (IIa), R 1 to R 5 four of which are independently selected from CN, CF3, a partially or fully perfluorinated C1 to C8 alkyl group, and the remainder are H or D.

[0082] According to one embodiment, in formula (II) and / or (IIa), R 1 to R 5 at least three of which are independently selected from CN, CF3, or a partially or fully perfluorinated C1 to C8 alkyl group, R 1 to R 5 at least one of which is selected from CN, and R 1 to R 5 at least one of which is selected from CF3 or a partially or fully perfluorinated C1 to C8 alkyl group.

[0083] According to one embodiment, in formula (II) and / or (IIa), R 1 to R 5 are independently selected from H, D, CN, or CF3, R 1 or R 5 at least one of which is selected from CN or CF3, R 1 to R 5 at least three of which are independently selected from CN or CF3, R 1 to R5 at least one of which is selected from CN, and R 1 to R 5 at least one of which is selected from CF3.

[0084] According to one embodiment, in formula (II) and / or (IIa), R 1 to R 5 are independently selected from H, D, CN or CF3.

[0085] According to one embodiment, in formula (II) and / or (IIa), R 1 to R 5 two of which are selected from CN.

[0086] According to one embodiment, in formula (II) and / or (IIa), R 1 to R 5 both are not CF3.

[0087] According to one embodiment, the compound of formula (I) and / or (Ia) contains 6 to 9 CN groups, preferably 9 CN groups.

[0088] According to one embodiment, the compound of formula (I) and / or (Ia) contains 3 to 9 CF3 groups or a partially or fully perfluorinated C1 to C8 alkyl group, more preferably 3 to 6 CF3 groups or a partially or fully perfluorinated C1 to C8 alkyl group, and most preferably 6 CF3 groups or a partially or fully perfluorinated C1 to C8 alkyl group.

[0089] According to one embodiment, the compound of formula (I) and / or (Ia) contains 6 to 9 CN groups and 3 to 9 CF3 groups or a partially or fully perfluorinated C1 to C8 alkyl group.

[0090] According to one embodiment, the compound of formula (I) and / or (Ia) contains 6 to 9 CN groups and 3 to 6 CF3 groups or a partially or fully perfluorinated C1 to C8 alkyl group.

[0091] According to one embodiment, the compound of formula (I) and / or (Ia) contains 6 to 9 CN groups and 6 CF3 groups or a partially or fully perfluorinated C1 to C8 alkyl group.

[0092] According to one embodiment, the compound of formula (I) and / or (Ia) contains 9 CN groups and 3 to 9 CF3 groups or a partially or fully perfluorinated C1 to C8 alkyl group.

[0093] According to one embodiment, the compound of formula (I) and / or (Ia) comprises 9 CN groups, and 3 to 6 CF3 groups or a partially or fully perfluorinated C1 to C8 alkyl group.

[0094] According to one embodiment, the compound of formula (I) or (Ia) comprises 9 CN groups and 6 CF3 groups or a partially or fully perfluorinated C1 to C8 alkyl group.

[0095] According to one embodiment, in formula (II) and / or (IIa), one or two of R 1 to R 5 are selected from H or D. Preferably, in formula (II), R k and R k+1 are selected from H or D, where k is 1 to 4.

[0096] According to one embodiment, in formula (II) and / or (IIa), one of R 1 to R 5 is selected from H or D.

[0097] According to one embodiment, in formula (II) and / or (IIa), one or two of R 2 or R 3 are selected from H or D.

[0098] According to one embodiment, in formula (II) and / or (IIa), one of R 2 or R 3 is selected from H or D.

[0099] According to one embodiment, in formula (II) and / or (IIa), R 1 and R 5 are independently selected from CN, CF3 or a partially or fully perfluorinated C1 to C8 alkyl.

[0100] According to one embodiment, in formula (II) and / or (IIa), R 1 and R 5 are independently selected from CN or CF3.

[0101] According to one embodiment, in formula (II) and / or (IIa), R 1 is CN, and R 5 is selected from CN, CF3 or a partially or fully perfluorinated C1 to C8 alkyl.

[0102] According to one embodiment, in formula (II) and / or (IIa), R 1 is CN, and R 5 is selected from CN or CF3.

[0103] According to one embodiment, the compound of formula (I) and / or (Ia) has a molecular weight of ≤ 1250 g / mol, preferably ≤ 1100 g / mol, more preferably ≤ 1070 g / mol.

[0104] According to one embodiment, the compound of formula (I) and / or (Ia) has a molecular weight of ≥ 500 g / mol to ≤ 1250 g / mol, preferably ≥ 550 g / mol to ≤ 1100 g / mol, more preferably ≥ 600 g / mol to ≤ 1070 g / mol.

[0105] During the manufacture of, for example, an organic electroluminescent device, the molecular weight within a given range of the compound of formula (Ia) or (IIa) enables the compound to be evaporated.

[0106] According to one embodiment, the compound of formula (I) and / or (Ia) has a molecular weight of ≤ 1250 g / mol, preferably ≤ 1100 g / mol, more preferably ≤ 1070 g / mol, and contains 6 to 9 CN groups, preferably 9 CN groups.

[0107] According to one embodiment, the compound of formula (I) and / or (Ia) has a molecular weight of ≥ 500 g / mol to ≤ 1250 g / mol, preferably ≥ 550 g / mol to ≤ 1100 g / mol, more preferably ≥ 600 g / mol to ≤ 1070 g / mol, contains 6 to 9 CN groups, preferably 9 CN groups.

[0108] According to one embodiment, the compound of formula (I) and / or (Ia) has a molecular weight of ≤ 1250 g / mol and contains 6 to 9 CN groups, preferably 9 CN groups.

[0109] According to one embodiment, the compound of formula (I) and / or (Ia) has a molecular weight of ≤ 1070 g / mol and contains 9 CN groups.

[0110] According to one embodiment, the compound of formula (I) and / or (Ia) has a molecular weight of ≥ 500 g / mol to ≤ 1250 g / mol, and wherein the compound of formula (Ia) or (IIa) contains 6 to 9 CN groups, preferably 9 CN groups.

[0111] According to one embodiment, wherein the compound of formula (I) and / or (Ia) has a molecular weight of ≥ 600 g / mol to ≤ 1070 g / mol, and wherein the compound of formula (Ia) or (IIa) contains 9 CN groups.

[0112] The molecular weight of the compound of formula (Ia) or (IIa) within a given range and a certain amount of CN groups further enable the evaporation of the compound to be improved during the manufacture of, for example, an organic light-emitting device.

[0113] According to one embodiment, the compound of formula (I) and / or (Ia) comprises a LUMO level, wherein the LUMO level is ≤ -4.65 eV, preferably ≤ -4.80 eV, more preferably ≤ -4.90 eV, more preferably ≤ -5.00 eV, more preferably ≤ -5.05 eV, more preferably ≤ -5.10 eV, and most preferably ≤ -5.15 eV.

[0114] The HOMO and LUMO were calculated using the program packages ORCA V5.0.3 (Max Planck Institute für Kohlenforschung, KaiserWilhelm Platz 1, 45470, Muelheim / Ruhr, Germany) and WEASEL 1.9.2 (FAccTs GmbH, Rolandstrasse 67, 50677 Germany). The dipole moment, HOMO, and LUMO levels of the molecular structure were determined from the optimized geometric configuration obtained by applying the hybrid functional B3LYP with the 6-31G* basis set in the gas phase. All calculations were carried out in the gas phase. If more than one conformation is feasible, the conformation with the lowest total energy was selected.

[0115] According to one embodiment, the compound of formula (I) and / or (Ia) comprises a LUMO level, wherein the LUMO level is ≥ -8.00 eV to ≤ -4.65 eV, preferably ≥ -7.50 eV to ≤ -4.80 eV, more preferably ≥ -7.75 eV to ≤ -4.90 eV, more preferably ≥ -7.50 eV to ≤ -5.00 eV, more preferably ≥ -7.25 eV to ≤ -5.05 eV, more preferably ≥ -7.00 eV to ≤ -5.10 eV, and most preferably ≥ -6.50 eV to ≤ -5.15 eV.

[0116] A low or deep LUMO level further enables the operating voltage of the organic light-emitting device to be reduced. The lower the LUMO level, the lower the operating voltage of the organic light-emitting device.

[0117] According to one embodiment, the compound of formula (I) and / or (Ia) has a LUMO level and a HOMO level, wherein the difference between the LUMO level and the HOMO level is ≥ 2.75 eV, preferably ≥ 2.80 eV, more preferably ≥ 2.85 eV, more preferably ≥ 2.90 eV, and most preferably ≥ 2.94 eV.

[0118] According to one embodiment, the compound of formula (I) and / or (Ia) has a LUMO energy level and a HOMO energy level, wherein the difference between the LUMO energy level and the HOMO energy level is ≥2.75 eV to ≤6.00 eV, preferably ≥2.80 eV to ≤5.50 eV, more preferably ≥2.85 eV to ≤5.00 eV, more preferably ≥2.90 eV to ≤4.50 eV, and most preferably ≥2.94 eV to ≤4.00 eV.

[0119] Compounds having a difference between the LUMO energy level and the HOMO energy level (energy gap (E-Gap)) within a given range have low absorption in the visible light range. The higher the difference between the LUMO energy level and the HOMO energy level, the higher the shift of the absorption in the direction of the blue region of the electromagnetic spectrum, and the lower the absorption in the visible light range in an organic electroluminescent device. Due to the lower absorption in the visible light range, the luminous flux, external quantum efficiency, or current efficiency of the organic electroluminescent device can be increased.

[0120] According to one embodiment, the compound of formula (I) and / or (Ia) has a molecular weight of ≤1100 g / mol and a LUMO energy level of ≤ -5.00 eV.

[0121] During the manufacture of, for example, an organic electroluminescent device, the molecules of the compound of formula (Ia) or (IIa) within a given range enable the compound to evaporate.

[0122] The low or deep LUMO energy level further enables the operating voltage of the organic electroluminescent device to be reduced. The lower the LUMO energy level, the lower the operating voltage of the organic electroluminescent device.

[0123] According to one embodiment, the compound of formula (I) and / or (Ia) has a molecular weight of ≥550 g / mol to ≤1100 g / mol and a LUMO energy level of ≤ -5.00 eV.

[0124] According to one embodiment, the compound of formula (I) and / or (Ia) has a molecular weight of ≥550 g / mol to ≤1100 g / mol and a LUMO energy level of ≥ -7.00 eV to ≤ -5.10 eV.

[0125] According to one embodiment, the compound of formula (I) and / or (Ia) has a molecular weight of ≤1100 g / mol and a LUMO energy level of ≤ -5.15 eV.

[0126] According to one embodiment, the compound of formula (I) and / or (Ia) has a molecular weight of ≥550 g / mol to ≤1100 g / mol and a LUMO energy level of ≤ -5.15 eV.

[0127] According to one embodiment, the compound of formula (I) and / or (Ia) has a molecular weight of ≥550 g / mol to ≤1100 g / mol and a LUMO energy level of ≥ -6.50 eV to ≤ -5.15 eV.

[0128] According to one embodiment, the compound of formula (I) and / or (Ia) has a molecular weight of ≤1100 g / mol and a LUMO energy level and a HOMO energy level, wherein the difference between the LUMO energy level and the HOMO energy level is ≥2.90 eV.

[0129] According to one embodiment, the compound of formula (I) and / or (Ia) has a molecular weight of ≥550 g / mol to ≤1100 g / mol and a LUMO energy level and a HOMO energy level, wherein the difference between the LUMO energy level and the HOMO energy level is ≥2.90 eV.

[0130] According to one embodiment, the compound of formula (I) and / or (Ia) has a molecular weight of ≥550 g / mol to ≤1100 g / mol and a LUMO energy level and a HOMO energy level, wherein the difference between the LUMO energy level and the HOMO energy level is ≥2.90 eV to ≤4.50 eV.

[0131] According to one embodiment, in formula (II) and / or (IIa), one or two of R 1 to R 5 are selected from H or D, and the corresponding compound of formula (I) and / or (Ia) has a LUMO energy level of ≤ -5.00 eV.

[0132] According to one embodiment, in formula (II) and / or (IIa), one or two of R 1 to R 5 are selected from H or D, and the corresponding compound of formula (I) and / or (Ia) has a LUMO energy level of ≥ -7.50 eV to ≤ -5.00 eV.

[0133] According to one embodiment, in formula (II) and / or (IIa), one or two of R 1 to R 5 are selected from H or D, and the corresponding compound of formula (I) and / or (Ia) has a LUMO energy level of ≤ -5.15 eV.

[0134] According to one embodiment, in formula (II) and / or (IIa), one or two of R 1 to R 5 are selected from H or D, and the corresponding compound of formula (I) and / or (Ia) has a LUMO energy level of ≥ -6.50 eV to ≤ -5.15 eV.

[0135] According to one embodiment, the compound of formula (I) and / or (Ia) has a LUMO energy level and a HOMO energy level, wherein the LUMO energy level is ≤ -4.65 eV, preferably ≤ -4.80 eV, more preferably ≤ -4.90 eV, more preferably ≤ -5.00 eV, more preferably ≤ -5.05 eV, more preferably ≤ -5.10 eV, most preferably ≤ -5.15 eV, and wherein the difference between the LUMO energy level and the HOMO energy level is ≥ 2.75 eV, preferably ≥ 2.80 eV, more preferably ≥ 2.85 eV, more preferably ≥ 2.90 eV, most preferably ≥ 2.94 eV.

[0136] According to one embodiment, the compound of formula (I) and / or (Ia) has a LUMO energy level and a HOMO energy level, wherein the LUMO energy level is ≥ -8.00 eV to ≤ -4.65 eV, preferably ≥ -7.50 eV to ≤ -4.80 eV, more preferably ≥ -7.75 eV to ≤ -4.90 eV, more preferably ≥ -7.50 eV to ≤ -5.00 eV, more preferably ≥ -7.25 eV to ≤ -5.05 eV, more preferably ≥ -7.00 eV to ≤ -5.10 eV, most preferably ≥ -6.50 eV to ≤ -5.15 eV, and wherein the difference between the LUMO energy level and the HOMO energy level is ≥ 2.75 eV to ≤ 6.00 eV, preferably ≥ 2.80 eV to ≤ 5.50 eV, more preferably ≥ 2.85 eV to ≤ 5.00 eV, more preferably ≥ 2.90 eV to ≤ 4.50 eV, most preferably ≥ 2.94 eV to ≤ 4.00 eV.

[0137] According to one embodiment, the compound of formula (I) and / or (Ia) has a LUMO energy level and a HOMO energy level, wherein the LUMO energy level is ≤ -4.65 eV, and wherein the difference between the LUMO energy level and the HOMO energy level is ≥ 2.75 eV.

[0138] According to one embodiment, the compound of formula (I) and / or (Ia) has a LUMO energy level and a HOMO energy level, wherein the LUMO energy level is ≥ -8.00 eV to ≤ -4.65 eV, and wherein the difference between the LUMO energy level and the HOMO energy level is ≥ 2.90 eV to ≤ 4.50 eV.

[0139] According to one embodiment, the compound of formula (I) and / or (Ia) has a LUMO energy level and a HOMO energy level, wherein the LUMO energy level is ≤ -4.90 eV, and wherein the difference between the LUMO energy level and the HOMO energy level is ≥ 2.90 eV.

[0140] According to one embodiment, the compound of formula (I) and / or (Ia) has a LUMO energy level and a HOMO energy level, wherein the LUMO energy level is ≥ -7.75 eV to ≤ -4.90 eV, and wherein the difference between the LUMO energy level and the HOMO energy level is ≥ 2.90 eV to ≤ 4.50 eV.

[0141] According to a most preferred embodiment, the compound of formula (I) and / or (Ia) has a LUMO energy level and a HOMO energy level, wherein the LUMO energy level is ≤ -5.15 eV, and wherein the difference between the LUMO energy level and the HOMO energy level is ≥ 2.94 eV.

[0142] According to a most preferred embodiment, the compound of formula (I) and / or (Ia) has a LUMO energy level and a HOMO energy level, wherein the LUMO energy level is ≥ -6.50 eV to ≤ -5.15 eV, and wherein the difference between the LUMO energy level and the HOMO energy level is ≥ 2.94 eV to ≤ 4.00 eV.

[0143] According to one embodiment, the compound of formula (I) and / or (Ia) has a molecular weight of ≤ 1100 g / mol and a LUMO energy level of ≤ -5.15 eV, and wherein the difference between the LUMO energy level and the HOMO energy level is ≥ 2.90 eV.

[0144] According to one embodiment, the compound of formula (I) and / or (Ia) has a molecular weight of ≥ 550 g / mol to ≤ 1100 g / mol and a LUMO energy level of ≤ -5.15 eV, and wherein the difference between the LUMO energy level and the HOMO energy level is ≥ 2.90 eV.

[0145] According to one embodiment, the compound of formula (I) and / or (Ia) has a molecular weight of ≥ 550 g / mol to ≤ 1100 g / mol, a LUMO energy level of ≥ -6.50 eV to ≤ -5.15 eV, and wherein the difference between the LUMO energy level and the HOMO energy level is ≥ 2.90 eV to ≤ 4.50 eV.

[0146] According to one embodiment, the compound of formula (I) and / or (Ia) has C3-symmetry.

[0147] According to one embodiment, the compound of formula (I) and / or (Ia) has the following structure (Ib):

[0148]

[0149] wherein B 1 has the following structure (IIc):

[0150]

[0151] The present invention also relates to a composition, which comprises a compound of formula (Ib) and a compound of formula (Ic).

[0152]

[0153] All references to the compounds of formula (I) and / or (Ia) are meant to include also this composition.

[0154] According to one embodiment, the moiety of formula (II) and / or formula (IIa) is selected from B1 to B26:

[0155]

[0156]

[0157]

[0158] According to one embodiment, the moiety of formula (II) and / or formula (IIa) is selected from B1 to B17.

[0159] According to a more preferred embodiment, the moiety of formula (II) and / or formula (IIa) is selected from B1 to B12.

[0160] According to a most preferred embodiment, the moiety of formula (II) and / or formula (IIa) is selected from B1 to B9.

[0161] According to one embodiment, the compound of formula (I) and / or (Ia) is selected from C1 to C26:

[0162]

[0163]

[0164]

[0165] According to one embodiment, the compound of formula (I) and / or (Ia) is selected from C1 to C17. According to one embodiment, the compound of formula (I) and / or (Ia) is selected from C1 to C12. According to one embodiment, the compound of formula (I) and / or (Ia) is selected from C1 to C9.

[0166] Organic electronic device

[0167] According to one embodiment of the present invention, the organic electronic device is an organic electroluminescent device; preferably an organic light emitting diode.

[0168] The present invention also relates to an organic electronic device, which comprises a first light emitting layer, a second light emitting layer and a charge generation layer.

[0169] According to one embodiment of the present invention, the organic electronic device is part of a display device.

[0170] According to one embodiment of the present invention, the organic electronic device is a pixel, particularly a pixel of a display device.

[0171] According to one embodiment of the present invention, the organic electronic device includes a first light-emitting layer, a second light-emitting layer, and a third light-emitting layer, or includes a first light-emitting layer, a second light-emitting layer, a third light-emitting layer, and a fourth light-emitting layer.

[0172] According to one embodiment of the present invention, the organic electronic device includes a first light-emitting layer, a second light-emitting layer, and a third light-emitting layer, or a first light-emitting layer, a second light-emitting layer, a third light-emitting layer, and a fourth light-emitting layer, a hole transport layer, and an electron transport layer.

[0173] According to one embodiment, the organic electroluminescent device further includes an electron transport layer, wherein the electron transport layer is disposed between the first light-emitting layer and the second light-emitting layer.

[0174] According to one embodiment, the organic electroluminescent device further includes an electron transport layer, wherein the electron transport layer is disposed between the first light-emitting layer and the second light-emitting layer, and wherein the electron transport layer is in direct contact with an n-type charge generation layer.

[0175] According to one embodiment, the organic electroluminescent device further includes a hole transport layer, wherein the hole transport layer is disposed between the first light-emitting layer and the second light-emitting layer.

[0176] According to one embodiment, the organic electroluminescent device further includes a hole transport layer, wherein the hole transport layer is disposed between the first light-emitting layer and the second light-emitting layer, wherein the hole transport layer is in direct contact with a p-type charge generation layer, and wherein the p-type charge generation layer includes a compound of formula (I).

[0177] According to one embodiment, the organic electroluminescent device further includes an electron transport layer and further includes a hole transport layer, wherein the electron transport layer is disposed between the first light-emitting layer and the second light-emitting layer, and wherein the hole transport layer is disposed between the first light-emitting layer and the second light-emitting layer.

[0178] According to one embodiment, the organic electroluminescent device further includes an electron transport layer and a hole transport layer, wherein the electron transport layer and the hole transport layer are disposed between the first light-emitting layer and the second light-emitting layer, wherein the electron transport layer is in direct contact with an n-type charge generation layer, and wherein the hole transport layer is in direct contact with a p-type charge generation layer, and wherein the p-type charge generation layer includes a compound of formula (I).

[0179] According to one embodiment, the p-type charge generation layer is in direct contact with the n-type charge generation layer, wherein the p-type charge generation layer contains the compound of formula (I).

[0180] According to one embodiment, the organic electroluminescent device further comprises an electron transport layer and a hole transport layer, wherein the electron transport layer and the hole transport layer are disposed between the first light-emitting layer and the second light-emitting layer, wherein the electron transport layer is in direct contact with the n-type charge generation layer, wherein the hole transport layer is in direct contact with the p-type charge generation layer, wherein the p-type charge generation layer is in direct contact with the n-type charge generation layer, and wherein the p-type charge generation layer contains the compound of formula (I).

[0181] According to one embodiment, the organic electroluminescent device further comprises a hole injection layer.

[0182] According to one embodiment, the organic electroluminescent device further comprises a hole injection layer, wherein the hole injection layer is adjacent to the anode layer.

[0183] According to one embodiment, the organic electroluminescent device further comprises a hole injection layer, wherein the hole injection layer is in direct contact with the anode layer.

[0184] According to one embodiment, the organic electroluminescent device further comprises a hole injection layer, wherein the hole injection layer contains the compound of formula (I).

[0185] According to one embodiment, the organic electroluminescent device further comprises a hole injection layer, wherein the hole injection layer contains the compound of formula (I), and wherein the hole injection layer is adjacent to the anode layer.

[0186] According to one embodiment, the organic electroluminescent device further comprises a hole injection layer, wherein the hole injection layer contains the compound of formula (I), and wherein the hole injection layer is in direct contact with the anode layer.

[0187] According to one embodiment, the organic electroluminescent device may comprise: a substrate; an anode layer; a hole injection layer; a first hole transport layer; a first electron blocking layer; a first light-emitting layer; an optional first hole blocking layer; a first electron transport layer; a charge generation layer, wherein the charge generation layer comprises an n-type charge generation layer and a p-type charge generation layer, and wherein the p-type charge generation layer contains the compound of formula (I); a second hole transport layer; a second electron blocking layer; a second light-emitting layer; a cathode layer, wherein an optional second hole blocking layer, an optional second electron transport layer, and / or an optional electron injection layer are disposed between the second light-emitting layer and the cathode layer.

[0188] According to one embodiment, the organic electroluminescent device may include: a substrate; an anode layer; a hole injection layer including a compound of formula (I); a first hole transport layer; a first electron blocking layer; a first light emitting layer; an optional first hole blocking layer; a first electron transport layer; a charge generation layer, wherein the charge generation layer includes an n-type charge generation layer and a p-type charge generation layer including a compound of formula (I); a second hole transport layer; a second electron blocking layer; a second light emitting layer; a cathode layer, wherein an optional second hole blocking layer, an optional second electron transport layer, and / or an optional electron injection layer are disposed between the second light emitting layer and the cathode layer, and wherein the compound of formula (I) in the hole injection layer and the compound of formula (I) in the p-type charge generation layer may be the same or different.

[0189] According to one embodiment, the organic electroluminescent device may include the following layer structure: a substrate, the substrate being disposed adjacent to the anode layer; a hole injection layer, the hole injection layer being disposed adjacent to the anode layer; a first hole transport layer, the first hole transport layer being disposed adjacent to the hole injection layer; a first electron blocking layer, the first electron blocking layer being disposed adjacent to the first hole transport layer; a first light emitting layer, the first light emitting layer being disposed adjacent to the first electron blocking layer; an optional first hole blocking layer, the optional first hole blocking layer being disposed adjacent to the first light emitting layer; a first electron transport layer, the first electron transport layer being disposed adjacent to the first light emitting layer or adjacent to the optional first hole blocking layer; a charge generation layer, the charge generation layer including an n-type charge generation layer and a p-type charge generation layer, the n-type charge generation layer being disposed adjacent to the first electron transport layer, the p-type charge generation layer including a compound of formula (I), the p-type charge generation layer being disposed adjacent to the n-type charge generation layer; a second hole transport layer, the second hole transport layer being disposed adjacent to the p-type charge generation layer; a second electron blocking layer, the second electron blocking layer being disposed adjacent to the second hole transport layer; a second light emitting layer, the second light emitting layer being disposed adjacent to the second electron blocking layer; a cathode layer, wherein an optional second hole blocking layer, an optional second electron transport layer, and / or an optional electron injection layer are disposed between the second light emitting layer and the cathode layer.

[0190] According to one embodiment, an organic electroluminescent device may include the following layer structure: a substrate, the substrate being disposed adjacent to an anode layer; a hole injection layer, the hole injection layer being disposed adjacent to the anode layer; a first hole transport layer, the first hole transport layer being disposed adjacent to the hole injection layer; a first electron blocking layer, the first electron blocking layer being disposed adjacent to the first hole transport layer; a first light emitting layer, the first light emitting layer being disposed adjacent to the first electron blocking layer; an optional first hole blocking layer, the optional first hole blocking layer being disposed adjacent to the first light emitting layer; a first electron transport layer, the first electron transport layer being disposed adjacent to the first light emitting layer or adjacent to the optional first hole blocking layer; a charge generation layer, the charge generation layer including an n-type charge generation layer and a p-type charge generation layer, the n-type charge generation layer being disposed adjacent to the first electron transport layer, the p-type charge generation layer including a compound of formula (Ia), the p-type charge generation layer being disposed adjacent to the n-type charge generation layer; a second hole transport layer, the second hole transport layer being disposed adjacent to the p-type charge generation layer; a second electron blocking layer, the second electron blocking layer being disposed adjacent to the second hole transport layer; a second light emitting layer, the second light emitting layer being disposed adjacent to the second electron blocking layer; an optional second hole blocking layer, the optional second hole blocking layer being disposed adjacent to the second light emitting layer; a second electron transport layer, the second electron transport layer being disposed adjacent to the second light emitting layer or adjacent to the optional second hole blocking layer; an electron injection layer, the electron injection layer being disposed adjacent to the second electron transport layer; and a cathode layer.

[0191] According to one embodiment, an organic electroluminescent device may include the following layer structure: a substrate, the substrate being disposed adjacent to an anode layer; a hole injection layer including a compound of formula (I), the hole injection layer being disposed adjacent to the anode layer; a first hole transport layer, the first hole transport layer being disposed adjacent to the hole injection layer; a first electron blocking layer, the first electron blocking layer being disposed adjacent to the first hole transport layer; a first light-emitting layer, the first light-emitting layer being disposed adjacent to the first electron blocking layer; an optional first hole blocking layer, the optional first hole blocking layer being disposed adjacent to the first light-emitting layer; a first electron transport layer, the first electron transport layer being disposed adjacent to the first light-emitting layer or adjacent to the optional first hole blocking layer; a charge generation layer, the charge generation layer including an n-type charge generation layer and a p-type charge generation layer, the n-type charge generation layer being disposed adjacent to the first electron transport layer, the p-type charge generation layer including a compound of formula (I), the p-type charge generation layer being disposed adjacent to the n-type charge generation layer; a second hole transport layer, the second hole transport layer being disposed adjacent to the p-type charge generation layer; a second electron blocking layer, the second electron blocking layer being disposed adjacent to the second hole transport layer; a second light-emitting layer, the second light-emitting layer being disposed adjacent to the second electron blocking layer; a cathode layer, an optional second hole blocking layer, an optional second electron transport layer, and / or an optional electron injection layer being disposed between the second light-emitting layer and the cathode layer, and the compound of formula (Ia) in the hole injection layer and the compound of formula (I) in the p-type charge generation layer may be the same or different.

[0192] According to one embodiment, the organic electroluminescent device may include the following layer structure: a substrate, the substrate being disposed adjacent to the anode layer; a hole injection layer including a compound of formula (I), wherein the hole injection layer is disposed adjacent to the anode layer; a first hole transport layer, wherein the first hole transport layer is disposed adjacent to the hole injection layer; a first electron blocking layer, wherein the first electron blocking layer is disposed adjacent to the first hole transport layer; a first light-emitting layer, wherein the first light-emitting layer is disposed adjacent to the first electron blocking layer; an optional first hole blocking layer, wherein the optional first hole blocking layer is disposed adjacent to the first light-emitting layer; a first electron transport layer, wherein the first electron transport layer is disposed adjacent to the first light-emitting layer or adjacent to the optional first hole blocking layer; a charge generation layer, wherein the charge generation layer includes an n-type charge generation layer and a p-type charge generation layer, wherein the n-type charge generation layer is disposed adjacent to the first electron transport layer, wherein the p-type charge generation layer includes a compound of formula (I), wherein the p-type charge generation layer is disposed adjacent to the n-type charge generation layer; a second hole transport layer, wherein the second hole transport layer is disposed adjacent to the p-type charge generation layer; a second electron blocking layer, wherein the second electron blocking layer is disposed adjacent to the second hole transport layer; a second light-emitting layer, wherein the second light-emitting layer is disposed adjacent to the second electron blocking layer; an optional second hole blocking layer, wherein the optional second hole blocking layer is disposed adjacent to the second light-emitting layer; a second electron transport layer, wherein the second electron transport layer is disposed adjacent to the second light-emitting layer or adjacent to the optional second hole blocking layer; an electron injection layer, wherein the electron injection layer is disposed adjacent to the second electron transport layer; a cathode layer, wherein the compound of formula (Ia) in the hole injection layer and the compound of formula (I) in the p-type charge generation layer may be the same or different.

[0193] According to one embodiment, an organic electroluminescent device may include the following layer structure: a substrate, the substrate being disposed adjacent to an anode layer; a hole injection layer including a compound of formula (I), wherein the hole injection layer is in direct contact with the anode layer; a first hole transport layer, wherein the first hole transport layer is in direct contact with the hole injection layer; a first electron blocking layer, wherein the first electron blocking layer is in direct contact with the first hole transport layer; a first light-emitting layer, wherein the first light-emitting layer is in direct contact with the first electron blocking layer; an optional first hole blocking layer, wherein the optional first hole blocking layer is in direct contact with the first light-emitting layer; a first electron transport layer, wherein the first electron transport layer is in direct contact with the first light-emitting layer or in direct contact with the optional first hole blocking layer; a charge generation layer, wherein the charge generation layer includes an n-type charge generation layer and a p-type charge generation layer, wherein the n-type charge generation layer is in direct contact with the first electron transport layer, wherein the p-type charge generation layer includes a compound of formula (Ia), wherein the p-type charge generation layer is in direct contact with the n-type charge generation layer; a second hole transport layer, wherein the second hole transport layer is in direct contact with the p-type charge generation layer; a second electron blocking layer, wherein the second electron blocking layer is in direct contact with the second hole transport layer; a second light-emitting layer, wherein the second light-emitting layer is in direct contact with the second electron blocking layer; a cathode layer, wherein an optional second hole blocking layer, an optional second electron transport layer, and / or an optional electron injection layer are disposed between the second light-emitting layer and the cathode layer, and wherein the compound of formula (I) in the hole injection layer and the compound of formula (I) in the p-type charge generation layer may be the same or different.

[0194] According to one embodiment, the organic electroluminescent device may include the following layer structure: a substrate, which is disposed adjacent to the anode layer; a hole injection layer including a compound of formula (I), wherein the hole injection layer is in direct contact with the anode layer; a first hole transport layer, wherein the first hole transport layer is in direct contact with the hole injection layer; a first electron blocking layer, wherein the first electron blocking layer is in direct contact with the first hole transport layer; a first light-emitting layer, wherein the first light-emitting layer is in direct contact with the first electron blocking layer; an optional first hole blocking layer, wherein the optional first hole blocking layer is in direct contact with the first light-emitting layer; a first electron transport layer, wherein the first electron transport layer is in direct contact with the first light-emitting layer or with the optional first hole blocking layer; a charge generation layer, wherein the charge generation layer includes an n-type charge generation layer and a p-type charge generation layer, wherein the n-type charge generation layer is in direct contact with the first electron transport layer, wherein the p-type charge generation layer includes a compound of formula (I), wherein the p-type charge generation layer is in direct contact with the n-type charge generation layer; a second hole transport layer, wherein the second hole transport layer is in direct contact with the p-type charge generation layer; a second electron blocking layer, wherein the second electron blocking layer is in direct contact with the second hole transport layer; a second light-emitting layer, wherein the second light-emitting layer is in direct contact with the second electron blocking layer; an optional second hole blocking layer, wherein the optional second hole blocking layer is in direct contact with the second light-emitting layer; a second electron transport layer, wherein the second electron transport layer is in direct contact with the second light-emitting layer or with the optional second hole blocking layer; an electron injection layer, wherein the electron injection layer is in direct contact with the second electron transport layer; a cathode layer, wherein the compound of formula (I) in the hole injection layer and the compound of formula (I) in the p-type charge generation layer may be the same or different.

[0195] According to one embodiment, the p-type charge generation layer including the compound of formula (I) further includes a hole transport matrix compound.

[0196] According to one embodiment, based on the total weight of the p-type charge generation layer, the amount of the compound of formula (I) present in the p-type charge generation layer is ≤99.9% by weight, preferably ≤99% by weight, more preferably ≤95% by weight, more preferably ≤90% by weight, more preferably ≤80% by weight, more preferably ≤70% by weight, more preferably ≤60% by weight, more preferably ≤50% by weight, more preferably ≤40% by weight, more preferably ≤30% by weight, more preferably ≤20% by weight, more preferably ≤10% by weight, more preferably ≤5% by weight.

[0197] According to one embodiment, based on the total weight of the p-type charge generation layer, the amount of the hole transport matrix compound present in the p-type charge generation layer is ≥0.1% by weight, preferably ≥1% by weight, more preferably ≥5% by weight, more preferably ≥10% by weight, more preferably ≥20% by weight, more preferably ≥30% by weight, more preferably ≥40% by weight, more preferably ≥50% by weight, more preferably ≥60% by weight, more preferably ≥70% by weight, more preferably ≥80% by weight, more preferably ≥90% by weight, more preferably ≥95% by weight.

[0198] According to one embodiment, based on the total weight of the p-type charge generation layer, the amount of the compound of formula (I) present in the p-type charge generation layer is ≤99.9% by weight, preferably ≤99% by weight, more preferably ≤95% by weight, more preferably ≤90% by weight, more preferably ≤80% by weight, more preferably ≤70% by weight, more preferably ≤60% by weight, more preferably ≤50% by weight, more preferably ≤40% by weight, more preferably ≤30% by weight, more preferably ≤20% by weight, more preferably ≤10% by weight, more preferably ≤5% by weight, and based on the total weight of the p-type charge generation layer, the amount of the hole transport matrix compound present in the p-type charge generation layer is ≥0.1% by weight, preferably ≥1% by weight, more preferably ≥5% by weight, more preferably ≥10% by weight, more preferably ≥20% by weight, more preferably ≥30% by weight, more preferably ≥40% by weight, more preferably ≥50% by weight, more preferably ≥60% by weight, more preferably ≥70% by weight, more preferably ≥80% by weight, more preferably ≥90% by weight, more preferably ≥95% by weight.

[0199] According to one embodiment, the organic electroluminescent device further includes a hole injection layer.

[0200] According to one embodiment, the organic electroluminescent device further includes a hole injection layer, wherein the hole injection layer contains the compound of formula (I).

[0201] According to one embodiment, the hole injection layer further includes a hole transport matrix compound.

[0202] According to one embodiment, the hole injection layer is adjacent to the anode layer.

[0203] According to one embodiment, the hole injection layer is in direct contact with the anode layer.

[0204] According to one embodiment, based on the total weight of the hole injection layer, the amount of the compound of formula (I) present in the hole injection layer is ≤99.9% by weight, preferably ≤99% by weight, more preferably ≤95% by weight, more preferably ≤90% by weight, more preferably ≤80% by weight, more preferably ≤70% by weight, more preferably ≤60% by weight, more preferably ≤50% by weight, more preferably ≤40% by weight, more preferably ≤30% by weight, more preferably ≤20% by weight, more preferably ≤10% by weight, more preferably ≤5% by weight, more preferably ≤3.0% by weight, more preferably ≤2.75% by weight, more preferably ≤2.5% by weight, more preferably ≤2.25% by weight, and most preferably ≤2.0% by weight.

[0205] According to one embodiment, based on the total weight of the hole injection layer, the amount of the hole transporting matrix compound present in the hole injection layer is ≥0.1% by weight, preferably ≥1% by weight, more preferably ≥5% by weight, more preferably ≥10% by weight, more preferably ≥20% by weight, more preferably ≥30% by weight, more preferably ≥40% by weight, more preferably ≥50% by weight, more preferably ≥60% by weight, more preferably ≥70% by weight, more preferably ≥80% by weight, more preferably ≥90% by weight, more preferably ≥95% by weight, more preferably ≥97.0% by weight, more preferably ≥97.25% by weight, more preferably ≥97.5% by weight, more preferably ≥97.75% by weight, and most preferably ≥98.0% by weight.

[0206] According to one embodiment, based on the total weight of the hole injection layer, the amount of the compound of formula (I) present in the hole injection layer is ≤99.9% by weight, preferably ≤99% by weight, more preferably ≤95% by weight, more preferably ≤90% by weight, more preferably ≤80% by weight, more preferably ≤70% by weight, more preferably ≤60% by weight, more preferably ≤50% by weight, more preferably ≤40% by weight, more preferably ≤30% by weight, more preferably ≤20% by weight, more preferably ≤10% by weight, more preferably ≤5% by weight, more preferably ≤3.0% by weight, more preferably ≤2.75% by weight, more preferably ≤2.5% by weight, more preferably ≤2.25% by weight, and most preferably ≤2.0% by weight, and based on the total weight of the hole injection layer, the amount of the hole transporting matrix compound present in the hole injection layer is ≥0.1% by weight, preferably ≥1% by weight, more preferably ≥5% by weight, more preferably ≥10% by weight, more preferably ≥20% by weight, more preferably ≥30% by weight, more preferably ≥40% by weight, more preferably ≥50% by weight, more preferably ≥60% by weight, more preferably ≥70% by weight, more preferably ≥80% by weight, more preferably ≥90% by weight, more preferably ≥95% by weight, more preferably ≥97.0% by weight, more preferably ≥97.25% by weight, more preferably ≥97.5% by weight, more preferably ≥97.75% by weight, and most preferably ≥98.0% by weight.

[0207] Hole transport matrix compound

[0208] The hole transporting matrix compound can be a substantially covalent matrix compound.

[0209] The substantially covalent matrix compound can be substantially composed of covalently bonded C, H, O, N, S, which optionally further contains covalently bonded B, P, As, and / or Se.

[0210] According to one embodiment, the substantially covalent matrix compound can be selected from organic compounds substantially composed of covalently bonded C, H, O, N, S, which optionally further contains covalently bonded B, P, As, and / or Se.

[0211] In one embodiment, the substantially covalent matrix compound has no metal atoms and most of its skeletal atoms can be selected from C, O, S, N. Alternatively, the substantially covalent matrix compound has no metal atoms and most of its skeletal atoms can be selected from C and N.

[0212] According to one embodiment of the present invention, the organic hole transporting compound contains at least 15 covalently bonded atoms, preferably at least 20 covalently bonded atoms, more preferably at least 25 covalently bonded atoms, more preferably at least 30 covalently bonded atoms, more preferably at least 35 covalently bonded atoms, more preferably 40 covalently bonded atoms, more preferably 45 covalently bonded atoms.

[0213] According to one embodiment, the substantially covalent matrix compound can have a molecular weight Mw of ≥400 g / mol and ≤2000 g / mol, preferably a molecular weight Mw of ≥450 g / mol and ≤1500 g / mol, further preferably a molecular weight Mw of ≥500 g / mol and ≤1000 g / mol, still preferably a molecular weight Mw of ≥550 g / mol and ≤900 g / mol, still preferably a molecular weight Mw of ≥600 g / mol and ≤800 g / mol.

[0214] Preferably, the substantially covalent matrix compound contains at least one arylamine moiety, or diarylamine moiety, or triarylamine moiety.

[0215] Preferably, the substantially covalent matrix compound has no metal and / or ionic bonds.

[0216] Compound of formula (IV) or compound of formula (V)

[0217] According to another aspect of the present invention, the substantially covalent matrix compound can contain at least one arylamine compound, diarylamine compound, triarylamine compound, compound of formula (IV) or compound of formula (V)

[0218]

[0219] Wherein:

[0220] T 1 、T 2 、T 3 、T 4 and T 5 are independently selected from a single bond, a phenylene, a biphenylene, a terphenylene or a naphthylene, preferably a single bond or a phenylene;

[0221] T 6 is a phenylene, a biphenylene, a terphenylene or a naphthylene;

[0222] Ar' 1 、Ar' 2 、Ar' 3 、Ar' 4 and Ar' 5 are independently selected from: substituted or unsubstituted C6 to C 20 aryl or substituted or unsubstituted C3 to C 20 heteroarylene; substituted or unsubstituted biphenylene; substituted or unsubstituted fluorene; substituted 9-fluorenyl; substituted 9,9-fluorenyl; substituted or unsubstituted naphthalene; substituted or unsubstituted anthracene; substituted or unsubstituted phenanthrene; substituted or unsubstituted pyrene; substituted or unsubstituted perylene; substituted or unsubstituted terphenylidene; substituted or unsubstituted tetracene; substituted or unsubstituted benzo(a)anthracene; substituted or unsubstituted dibenzofuran; substituted or unsubstituted dibenzothiophene; substituted or unsubstituted xanthene; substituted or unsubstituted carbazole; substituted 9-phenylcarbazole; substituted or unsubstituted azepine; substituted or unsubstituted dibenzo[b,f]azepine; substituted or unsubstituted 9,9'-spirobi[fluorene]; substituted or unsubstituted spiro[fluorene-9,9'-xanthene]; or a substituted or unsubstituted aromatic fused ring system comprising at least three substituted or unsubstituted aromatic rings selected from substituted or unsubstituted non-heterocyclic, substituted or unsubstituted hetero 5-membered rings, substituted or unsubstituted 6-membered rings and / or substituted or unsubstituted 7-membered rings, substituted or unsubstituted fluorene; or a fused ring system comprising 2 to 6 substituted or unsubstituted 5- to 7-membered rings, and the rings are selected from: (i) unsaturated 5- to 7-membered heterocyclic rings; (ii) 5- to 6-membered aromatic heterocyclic rings; (iii) unsaturated 5- to 7-membered non-heterocyclic rings; (iv) 6-membered aromatic non-heterocyclic rings;

[0223] Wherein

[0224] Ar' 1 、Ar' 2 、Ar' 3 、Ar' 4 and Ar' 5The substituents are the same or different and are selected from: H, D, F, C(=O)R 2 , CN, Si(R 2 )3, P(=O)(R 2 )2, OR 2 , S(=O)R 2 , S(=O)2R 2 , a substituted or unsubstituted straight-chain alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted branched-chain alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cyclic alkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl or alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aromatic ring system having 6 to 40 aromatic ring atoms, and a substituted or unsubstituted heteroaromatic ring system having 5 to 40 aromatic ring atoms, unsubstituted C6 to C 18 aryl, unsubstituted C3 to C 18 heteroaryl, a fused ring system containing 2 to 6 unsubstituted 5- to 7-membered rings, and the rings are selected from: an unsaturated 5- to 7-membered heterocyclic ring, a 5- to 6-membered aromatic heterocyclic ring, an unsaturated 5- to 7-membered non-heterocyclic ring, and a 6-membered aromatic non-heterocyclic ring,

[0225] wherein R 2 can be selected from H, D, a straight-chain alkyl group having 1 to 6 carbon atoms, a branched-chain alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 6 carbon atoms, an alkenyl or alkynyl group having 2 to 6 carbon atoms, C6 to C 18 aryl or C3 to C 18 heteroaryl.

[0226] According to one embodiment, wherein T 1 , T 2 , T 3 , T 4 and T 5 can independently be selected from a single bond, a phenylene group, a biphenylene group, or a terphenylene group. According to one embodiment, wherein T 1 , T 2 , T 3 , T 4 and T 5 can independently be selected from a phenylene group, a biphenylene group, or a terphenylene group, and one of T 1 , T 2 , T 3 , T 4 and T 5 is a single bond. According to one embodiment, wherein T 1 , T 2 , T 3 , T 4 and T 5may be independently selected from phenylene or biphenylene, and T 1 、T 2 、T 3 、T 4 and T 5 is a single bond. According to one embodiment, wherein T 1 、T 2 、T 3 、T 4 and T 5 may be independently selected from phenylene or biphenylene, and T 1 、T 2 、T 3 、T 4 and T 5 are two single bonds.

[0227] According to one embodiment, wherein T 1 、T 2 and T 3 may be independently selected from phenylene, and T 1 、T 2 and T 3 is a single bond. According to one embodiment, wherein T 1 、T 2 and T 3 may be independently selected from phenylene, and T 1 、T 2 and T 3 are two single bonds.

[0228] According to one embodiment, wherein T 6 may be phenylene, biphenylene, terphenylenylene. According to one embodiment, wherein T 6 may be phenylene. According to one embodiment, wherein T 6 may be biphenylene. According to one embodiment, wherein T 6 may be terphenylenylene.

[0229] According to one embodiment, wherein Ar' 1 、Ar' 2 、Ar' 3 、Ar' 4 and Ar' 5 may be independently selected from D1 to D16:

[0230]

[0231] wherein the asterisk "*" represents the binding position.

[0232] According to one embodiment, wherein Ar' 1 、Ar' 2, Ar' 3 , Ar' 4 and Ar' 5 may be independently selected from D1 to D15; or selected from D1 to D10 and D13 to D15.

[0233] According to one embodiment, wherein Ar' 1 , Ar' 2 , Ar' 3 , Ar' 4 and Ar' 5 may be independently selected from D1, D2, D5, D7, D9, D10, D13 to D16.

[0234] When Ar' 1 , Ar' 2 , Ar' 3 , Ar' 4 and Ar' 5 is selected within this range, the standard starting temperature can be within a range particularly suitable for large-scale production.

[0235] According to one embodiment, the substantially covalent matrix compound comprises at least one naphthyl group, carbazole group, dibenzofuran group, dibenzothiophene group and / or substituted fluorene group, wherein the substituents are independently selected from methyl, phenyl or fluorene group.

[0236] According to one embodiment of the present invention, the matrix compound of formula (IV) or formula (V) is selected from F1 to F21:

[0237]

[0238]

[0239]

[0240] Display device

[0241] The present invention also relates to a display device, the display device comprising a plurality of organic electronic devices according to the present invention, wherein at least two of the plurality of organic electronic devices share a common charge generation layer as the charge generation layer.

[0242] The present invention also relates to a display device, the display device comprising a plurality of organic electronic devices according to the present invention, wherein at least two of the plurality of organic electronic devices share a common charge generation layer as the charge generation layer.

[0243] The present invention also relates to a display device, which comprises a plurality of organic electronic devices according to the present invention, wherein at least two of the plurality of organic electronic devices share a common charge generation layer extending above at least two of the plurality of organic electronic devices as a charge generation layer.

[0244] The present invention also relates to a display device, which comprises a plurality of organic electronic devices according to the present invention, wherein at least two of the plurality of organic electronic devices share a common charge generation layer extending above at least two of the plurality of organic electronic devices as a charge generation layer.

[0245] The present invention also relates to a display device, which comprises a plurality of organic electroluminescent devices according to the present invention, wherein each of the plurality of electroluminescent devices shares a common charge generation layer extending above all of the plurality of organic electroluminescent devices as a charge generation layer.

[0246] The present invention also relates to a display device, which comprises a plurality of organic electroluminescent devices according to the present invention, wherein each of the plurality of organic electroluminescent devices shares a common charge generation layer extending above all of the plurality of organic electroluminescent devices as a charge generation layer.

[0247] In other words, the present invention relates to a display device, which comprises a charge generation layer according to the present invention, wherein a plurality of at least two vertically stacked electroluminescent units are horizontally arranged with respect to the charge generation layer. Thus, each of the at least two vertically stacked electroluminescent units forms an organic electroluminescent device according to the present invention together with the common charge generation layer.

[0248] According to one embodiment of the present invention, each electroluminescent device comprises at least three or at least four vertically stacked electroluminescent units, wherein each electroluminescent unit comprises at least one light-emitting layer.

[0249] According to one embodiment of the present invention, the display device is an active matrix display.

[0250] According to one embodiment of the present invention, the display device is an OLED display.

[0251] According to one embodiment of the present invention, the display device comprises a driving circuit configured to separately drive pixels in a plurality of pixels.

[0252] Other layers

[0253] According to the present invention, the organic electroluminescent device or the display device is further referred to as an organic electronic device or apparatus, and may further comprise other layers in addition to the layers already mentioned above. Exemplary embodiments of each layer are described below:

[0254] N-type charge generation layer

[0255] According to one embodiment of the present invention, the n-type charge generation layer comprises an electron transport material.

[0256] According to one embodiment of the present invention, the n-type charge generation layer further comprises an organic electron transport material.

[0257] According to one embodiment of the present invention, the electron transport material comprises at least one C2 to C 24 N-heteroaryl or P═X group, where X is O, P, Se, and P═O is particularly preferred.

[0258] According to one embodiment of the present invention, at least one C2 to C 24 N-heteroaryl may be selected from compounds comprising at least one azine group, preferably at least two azine groups, more preferably three azine groups.

[0259] According to one embodiment of the present invention, the electron transport material comprises at least one group selected from the following groups: pyridine, pyrimidine, triazine, imidazole, benzimidazole, benzo oxazole, quinone, benzoquinone, imidazo[1,5-a]pyridine, quinoxaline, benzoquinoxaline, acridine, phenanthroline, benzacridine, dibenzacridine, phosphine oxide, tripyridine.

[0260] According to one embodiment of the present invention, the electron transport material comprises at least one phenanthroline group, preferably two phenanthroline groups; one or more pyridine groups; one or more pyrimidine groups; one or more triazine groups; one or more imidazo[1,5-a]pyridine groups; or one or more phosphine oxide groups.

[0261] According to one embodiment of the present invention, the organic electron transport material comprises at least one phenanthroline group, preferably two phenanthroline groups; one or more pyridine groups; one or more pyrimidine groups; or one or more phosphine oxide groups.

[0262] According to one embodiment of the present invention, the electron transport material comprises at least one phenanthroline group, preferably two phenanthroline groups; pyridine group; pyrimidine group; or phosphine oxide group.

[0263] According to one embodiment of the present invention, the electron transport material compound comprises at least one phenanthroline group, preferably two phenanthroline groups; one or more pyridine groups; one or more pyrimidine groups; one or more triazine groups.

[0264] According to one embodiment of the present invention, the electron transport material is selected from 2,2'-(1,3-phenylene)bis[9-phenyl-1,10-phenanthroline], (3-(10-(3-(2,6-diphenylpyrimidin-4-yl)phenyl)anthracen-9-yl)phenyl)dimethylphosphine oxide, 3-(3-(9,10-diphenylanthracen-2-yl)phenyl)-1-(pyridin-2-yl)imidazo[1,5-a]pyridine, 7-(3-(1,10-phenanthrolin-2-yl)phenyl)dibenzo[c,h]acridine, 7-(3-([2,2':6',2”-terpyridine]-4'-yl)phenyl)dibenzo[c,h]acridine, 4'-(4'-(4,6-diphenyl-1,3,5-triazin-2-yl)-[1,1'-biphenyl]-4-yl)-2,2':6',2”-terpyridine, 4'-(4-(fluoranthen-3-yl)phenyl)-2,2':6',2”-terpyridine or 3-(9,10-di-2-naphthalen-2-yl-2-anthracenyl)phenyl]dimethylphosphine oxide.

[0265] According to one embodiment of the present invention, the electron transport material contains at least one phenanthroline group, preferably two phenanthroline groups.

[0266] According to one embodiment of the present invention, the n-type charge generation layer contains a metal dopant.

[0267] According to one embodiment of the present invention, the metal dopant is selected from metals having an electronegativity of ≤1.4 eV according to the Pauling scale, or metal alloys containing metals having an electronegativity of ≤1.4 eV according to the Pauling scale.

[0268] According to one embodiment of the present invention, the metal dopant is selected from metals having an electronegativity of ≤1.35 eV according to the Pauling scale, or metal alloys containing metals having an electronegativity of ≤1.35 eV according to the Pauling scale.

[0269] According to one embodiment of the present invention, the metal dopant is a metal selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sm, Eu and Yb, or a metal alloy containing a metal selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sm, Eu and Yb.

[0270] According to one embodiment of the present invention, the metal dopant is a metal selected from Li, Na, K, Cs, Mg, Ca, Ba, Sm, Eu and Yb, or a metal alloy containing a metal selected from Li, Na, K, Cs, Mg, Ca, Ba, Sm, Eu and Yb.

[0271] According to an embodiment of the present invention, the metal dopant is a metal selected from Li, Mg, and Yb, or a metal alloy containing a metal selected from Li, Mg, and Yb.

[0272] According to an embodiment of the present invention, the metal dopant is a metal selected from Li and Yb, or a metal alloy containing a metal selected from Li and Yb.

[0273] According to an embodiment of the present invention, the metal dopant is Yb, or a metal alloy containing a metal selected from Li and Yb.

[0274] According to an embodiment of the present invention, the metal dopant is Yb.

[0275] According to an embodiment of the present invention, the amount of the metal dopant present in the n-type charge generation layer is ≤99.9 wt%, preferably ≤99 wt%, more preferably ≤95 wt%, more preferably ≤90 wt%, more preferably ≤80 wt%, more preferably ≤70 wt%, more preferably ≤60 wt%, more preferably ≤50 wt%, more preferably ≤40 wt%, more preferably ≤30 wt%, more preferably ≤20 wt%, more preferably ≤10 wt%, more preferably ≤5 wt%, more preferably ≤3.0 wt%, more preferably ≤2.75 wt%, more preferably ≤2.5 wt%, more preferably ≤2.25 wt%, and most preferably ≤2.0 wt% based on the total weight of the layer.

[0276] According to an embodiment of the present invention, the amount of the electron transport material present in the n-type charge generation layer is ≥0.1 wt%, preferably ≥1 wt%, more preferably ≥5 wt%, more preferably ≥10 wt%, more preferably ≥20 wt%, more preferably ≥30 wt%, more preferably ≥40 wt%, more preferably ≥50 wt%, more preferably ≥60 wt%, more preferably ≥70 wt%, more preferably ≥80 wt%, more preferably ≥90 wt%, more preferably ≥95 wt%, more preferably ≥97.0 wt%, more preferably ≥97.25 wt%, more preferably ≥97.5 wt%, more preferably ≥97.75 wt%, and most preferably ≥98.0 wt% based on the total weight of the layer.

[0277] Substrate

[0278] The substrate can be any substrate commonly used in the manufacture of electronic devices such as organic light-emitting diodes. If light is to be emitted through the substrate, the substrate should be a transparent or translucent material, such as a glass substrate or a transparent plastic substrate. If light is to be emitted through the top surface, the substrate can be a transparent as well as an opaque material, such as a glass substrate, a plastic substrate, a metal substrate, or a silicon substrate.

[0279] Anode layer

[0280] The anode layer can be formed by depositing or sputtering a material for forming the anode layer. The material for forming the anode layer can be a high work function material to facilitate hole injection. The anode material can also be selected from low work function materials (i.e., aluminum). The anode electrode can be a transparent or reflective electrode. Transparent conductive oxides such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2), aluminum zinc oxide (AlZO), and zinc oxide (ZnO) can be used to form the anode electrode. The anode layer can also be formed using a metal, typically silver (Ag), gold (Au), or a metal alloy.

[0281] Hole transport layer

[0282] The hole transport layer (HTL) can be formed on the HIL by vacuum deposition, spin coating, slot die coating, printing, casting, Langmuir-Blodgett (LB) deposition, etc. When forming the HTL by vacuum deposition or spin coating, the deposition and coating conditions can be similar to those for forming the HIL. However, the vacuum or solution deposition conditions can vary depending on the compound used to form the HTL.

[0283] The HTL can be formed from any compound commonly used to form an HTL. For example, compounds suitable for use are disclosed in Yasuhiko Shirota and Hiroshi Kageyama, Chem. Rev. 2007, 107, 953 - 1010 and are incorporated herein by reference. Examples of compounds that can be used to form the HTL are: carbazole derivatives such as N-phenylcarbazole or polyvinylcarbazole; benzidine derivatives such as N,N'-bis(3-methylphenyl)-N,N'-diphenyl-[1,1-biphenyl]-4,4'-diamine (TPD) or N,N'-bis(naphthalen-1-yl)-N,N'-diphenylbenzidine (α-NPD); and triphenylamine compounds such as 4,4',4''-tris(N-carbazolyl)triphenylamine (TCTA). Among these compounds, TCTA can transport holes and inhibit exciton diffusion into the EML.

[0284] According to one embodiment of the present invention, the hole transport layer can comprise a substantially covalent matrix compound as described above.

[0285] According to one embodiment of the present invention, the hole transport layer can comprise a compound of formula (VI) or (VII) as described above.

[0286] According to a preferred embodiment of the present invention, the hole injection layer and the hole transport layer can comprise the same compound of formula (VI) or (VII) as described above.

[0287] According to a preferred embodiment of the present invention, the p-type charge generation layer, the hole injection layer, and the hole transport layer may comprise the same substantially covalent matrix compound.

[0288] According to a preferred embodiment of the present invention, the p-type charge generation layer, the hole injection layer, and the hole transport layer may comprise the same compound of formula (IV) or (V) as described above.

[0289] The thickness of the HTL may be in the range of about 5 nm to about 250 nm, preferably about 10 nm to about 200 nm, further about 20 nm to about 190 nm, further about 40 nm to about 180 nm, further about 60 nm to about 170 nm, further about 80 nm to about 160 nm, further about 100 nm to about 160 nm, further about 120 nm to about 140 nm. The preferred thickness of the HTL may be 170 nm to 200 nm.

[0290] When the thickness of the HTL is within this range, the HTL may have excellent hole transport characteristics without substantial impairment to the driving voltage.

[0291] Electron blocking layer

[0292] The function of the electron blocking layer (EBL) is to prevent electrons from transferring from the light-emitting layer to the hole transport layer, thereby confining the electrons in the light-emitting layer. As a result, the efficiency, operating voltage, and / or lifetime are improved. Generally, the electron blocking layer comprises a triarylamine compound. The LUMO energy level of the triarylamine compound may be closer to the vacuum energy level than the LUMO energy level of the hole transport layer. Compared with the HOMO energy level of the hole transport layer, the electron blocking layer may have a HOMO energy level that is further from the vacuum energy level. The thickness of the electron blocking layer may be selected between 2 nm and 20 nm.

[0293] If the electron blocking layer has a high triplet energy level, it may also be described as a triplet control layer.

[0294] If a phosphorescent green or blue light-emitting layer is used, the function of the triplet control layer is to reduce the quenching of triplets. As a result, a higher luminescence efficiency of the phosphorescent light-emitting layer can be achieved. The triplet control layer is selected from triarylamine compounds having a triplet energy level higher than the triplet energy level of the phosphorescent emitter in the adjacent light-emitting layer. Suitable compounds for the triplet control layer, in particular triarylamine compounds, are described in EP 2 722 908 A1.

[0295] Photoactive layer (PAL)

[0296] According to an embodiment of the present invention, the organic electronic device may further comprise a photoactive layer, wherein the photoactive layer is disposed between the anode layer and the cathode layer.

[0297] The photoactive layer converts current into photons or photons into current.

[0298] The PAL can be formed on the HTL by vacuum deposition, spin coating, slot die coating, printing, casting, LB deposition, etc. When vacuum deposition or spin coating is used to form the PAL, the deposition and coating conditions can be similar to those for forming the HIL. However, the deposition and coating conditions can vary depending on the compound used to form the PAL.

[0299] According to one embodiment of the present invention, the photoactive layer does not contain the compound of formula (I).

[0300] The photoactive layer can be a light-emitting layer or a light-absorbing layer.

[0301] Light-emitting layer (EML)

[0302] According to one embodiment of the present invention, the organic electronic device may further include a light-emitting layer, wherein the light-emitting layer is disposed between the anode layer and the cathode layer.

[0303] The EML can be formed on the HTL by vacuum deposition, spin coating, slot die coating, printing, casting, LB deposition, etc. When vacuum deposition or spin coating is used to form the EML, the deposition and coating conditions can be similar to those for forming the HIL. However, the deposition and coating conditions can vary depending on the compound used to form the EML.

[0304] According to one embodiment of the present invention, the light-emitting layer does not contain the compound of formula (I).

[0305] The light-emitting layer (EML) can be formed by a combination of a host and a luminescent dopant. Examples of the host are: Alq3, 4,4'-N,N'-dicarbazole-biphenyl (CBP), poly(n-vinylcarbazole) (PVK), 9,10-bis(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), stilbenylarylidene (DSA), and zinc bis(2-(2-hydroxyphenyl)benzothiazole) (Zn(BTZ)2).

[0306] The luminescent dopant can be a phosphorescent or fluorescent emitter. Phosphorescent emitters and emitters that emit light via the thermally activated delayed fluorescence (TADF) mechanism may be preferred due to their higher efficiency. The emitter can be a small molecule or a polymer.

[0307] Examples of red light-emitting dopants are PtOEP, Ir(piq)3, and Btp2Ir(acac), but are not limited thereto. These compounds are phosphorescent light emitters; however, fluorescent red light-emitting dopants may also be used.

[0308] Examples of phosphorescent green light-emitting dopants are Ir(ppy)3 (ppy = phenylpyridine), Ir(ppy)2(acac), and Ir(mpyp)3.

[0309] Examples of phosphorescent blue light-emitting dopants are: F2Irpic, (F2ppy)2Ir(tmd), and Ir(dfppz)3; and tris(9,9-difluorenyl)amine. Examples of fluorescent blue light-emitting dopants are 4,4'-bis(4-diphenylaminostyryl)biphenyl (DPAVBi), 2,5,8,11-tetra-tert-butylperylene (TBPe).

[0310] Based on 100 parts by weight of the host, the amount of the light-emitting dopant can range from about 0.01 part by weight to about 50 parts by weight. Alternatively, the light-emitting layer may be composed of a light-emitting polymer. The thickness of the EML can be from about 10 nm to about 100 nm, for example, from about 20 nm to about 60 nm. When the thickness of the EML is within this range, the EML can have excellent light emission without substantial impairment of the driving voltage.

[0311] Hole blocking layer (HBL)

[0312] The hole blocking layer (HBL) can be formed on the EML by using vacuum deposition, spin coating, slot die coating, printing, casting, LB deposition, etc. to prevent holes from diffusing into the ETL. When the EML contains a phosphorescent dopant, the HBL can also have a triplet exciton blocking function.

[0313] The HBL can also be referred to as an auxiliary ETL or a-ETL.

[0314] When vacuum deposition or spin coating is used to form the HBL, the deposition and coating conditions can be similar to those used for forming the HIL. However, the deposition and coating conditions can vary depending on the compound used for forming the HBL. Any compound commonly used for forming the HBL can be used. Examples of compounds used for forming the HBL include diazole derivatives, triazole derivatives, phenanthroline derivatives, and azine derivatives, preferably triazine or pyrimidine derivatives.

[0315] The thickness of the HBL can be in the range of about 5 nm to about 100 nm, for example, from about 10 nm to about 30 nm. When the thickness of the HBL is within this range, the HBL can have excellent hole blocking properties without substantial impairment of the driving voltage.

[0316] Electron Transport Layer (ETL)

[0317] The organic electronic device according to the present invention may further include an electron transport layer (ETL).

[0318] According to another embodiment of the present invention, the electron transport layer may further include an azine compound, preferably a triazine compound or a pyrimidine compound.

[0319] In one embodiment, the electron transport layer may further include a dopant selected from alkali metal organic complexes, preferably LiQ.

[0320] The thickness of the ETL may be in the range of about 15 nm to about 50 nm, for example, in the range of about 20 nm to about 40 nm. When the thickness of the ETL is within this range, the ETL may have satisfactory electron injection characteristics without substantial damage to the driving voltage.

[0321] According to another embodiment of the present invention, the organic electronic device may further include a hole blocking layer and an electron transport layer, wherein the hole blocking layer and the electron transport layer contain an azine compound. Preferably, the azine compound is a triazine compound.

[0322] According to one embodiment of the present invention, the n-type charge generation layer is sandwiched between the electron transport layer and the p-type charge generation layer.

[0323] According to one embodiment of the present invention, the n-type charge generation layer is sandwiched between the electron transport layer and the p-type charge generation layer; wherein the n-type charge generation layer and / or the electron transport layer contains an azine compound. Particularly improved performance can be obtained.

[0324] According to one embodiment of the present invention, the n-type charge generation layer is sandwiched between the electron transport layer and the p-type charge generation layer; and the electron transport layer is sandwiched between the first light-emitting layer and the n-type charge generation layer; wherein the n-type charge generation layer and / or the electron transport layer contains an azine compound. Particularly improved performance can be obtained.

[0325] According to one embodiment of the present invention, the n-type charge generation layer is sandwiched between the electron transport layer and the p-type charge generation layer; and the electron transport layer is sandwiched between the first light-emitting layer and the n-type charge generation layer; wherein the n-type charge generation layer contains a phenanthroline compound and the electron transport layer contains an azine compound, preferably a triazine or pyrimidine compound. Particularly improved performance can be obtained.

[0326] Electron Injection Layer (EIL)

[0327] An optional EIL that can facilitate electron injection from the cathode can be formed on the ETL, preferably directly on the electron transport layer. Examples of materials for forming the EIL include lithium 8-hydroxyquinoline (LiQ), LiF, NaCl, CsF, Li2O, BaO, Ca, Ba, Yb, Mg known in the art. The deposition and coating conditions for forming the EIL are similar to those for forming the HIL, but the deposition and coating conditions can vary depending on the material used to form the EIL.

[0328] The thickness of the EIL can be in the range of about 0.1 nm to about 10 nm, for example, in the range of about 0.5 nm to about 9 nm. When the thickness of the EIL is within this range, the EIL can have satisfactory electron injection properties without substantial impairment of the driving voltage.

[0329] Cathode layer

[0330] The cathode layer is formed on the ETL or the optional EIL. The cathode layer can be formed of a metal, an alloy, a conductive compound, or a mixture thereof. The cathode electrode can have a low work function. For example, the cathode layer can be formed of lithium (Li), magnesium (Mg), aluminum (Al), aluminum (Al)-lithium (Li), calcium (Ca), barium (Ba), ytterbium (Yb), magnesium (Mg)-indium (In), magnesium (Mg)-silver (Ag), etc. Alternatively, the cathode electrode can be formed of a transparent conductive oxide such as ITO or IZO.

[0331] The thickness of the cathode layer can be in the range of about 5 nm to about 1000 nm, for example, in the range of about 10 nm to about 100 nm. When the thickness of the cathode layer is in the range of about 5 nm to about 50 nm, even if the cathode layer is formed of a metal or a metal alloy, it can be transparent or semi-transparent.

[0332] It should be understood that the cathode layer is not part of the electron injection layer or the electron transport layer.

[0333] Organic semiconductor layer and device comprising the same

[0334] The present invention also relates to an organic semiconductor layer, wherein the organic semiconductor layer contains a compound of formula (Ia).

[0335] According to one embodiment, the organic semiconductor layer contains a compound of formula (Ia) and a hole transport matrix compound.

[0336] According to one embodiment, the organic semiconductor layer is a hole injection layer or a p-type charge generation layer.

[0337] The present invention also relates to an organic electronic device, which comprises the organic semiconductor layer as described above.

[0338] According to one embodiment, an organic electronic device includes an anode layer, a cathode layer, and at least one organic semiconductor layer, wherein the organic semiconductor layer is disposed between the anode layer and the cathode layer.

[0339] According to one embodiment, an organic electronic device includes an anode layer, a cathode layer, and at least one organic semiconductor layer, wherein the organic semiconductor layer is disposed between the anode layer and the cathode layer, and wherein the organic semiconductor layer is a hole injection layer or a p-type charge generation layer.

[0340] According to one embodiment, an organic electronic device includes an anode layer, a cathode layer, and at least one organic semiconductor layer, wherein the organic semiconductor layer is disposed between the anode layer and the cathode layer, and wherein at least one organic semiconductor layer is a hole injection layer and / or a p-type charge generation layer.

[0341] According to one embodiment, an organic electronic device includes an anode layer, a cathode layer, and at least one organic semiconductor layer, wherein the organic semiconductor layer is disposed between the anode layer and the cathode layer, and wherein at least one organic semiconductor layer is a hole injection layer and a p-type charge generation layer.

[0342] According to one embodiment, the organic electronic device is an electroluminescent device, an organic electroluminescent device, an organic light emitting diode (OLED), a light emitting device, a thin film transistor, a battery, an organic photovoltaic cell (OPV), or an organic solar cell, preferably an organic electroluminescent device, an organic light emitting diode (OLED), a light emitting device, more preferably an organic electroluminescent device or an organic light emitting diode (OLED).

[0343] According to one embodiment, the organic electronic device is an organic electroluminescent device.

[0344] According to one embodiment, the organic semiconductor layer of the compound of formula (Ia) in the organic electronic device is a hole injection layer, wherein the hole injection layer is adjacent to the anode layer.

[0345] According to one embodiment, the organic semiconductor layer of the compound of formula (Ia) in the organic electronic device is a hole injection layer, wherein the hole injection layer is in direct contact with the anode layer.

[0346] According to one embodiment, the organic electroluminescent device includes: a substrate; an anode layer formed on the substrate; an organic semiconductor layer of the compound of formula (Ia), wherein the organic semiconductor layer is a hole injection layer; a light emitting layer; and a cathode layer, wherein the hole injection layer and the light emitting layer are disposed between the anode layer and the cathode layer, and wherein the hole injection layer is disposed between the anode layer and the light emitting layer.

[0347] According to one embodiment, an organic electroluminescent device includes: a substrate; an anode layer formed on the substrate; an organic semiconductor layer including a compound of Formula (Ia), wherein the organic semiconductor layer is a hole injection layer; a light-emitting layer; and a cathode layer, wherein the hole injection layer and the light-emitting layer are disposed between the anode layer and the cathode layer, wherein the hole injection layer is disposed between the anode layer and the light-emitting layer, and wherein the hole injection layer is adjacent to the anode layer.

[0348] According to one embodiment, an organic electroluminescent device includes: a substrate; an anode layer formed on the substrate; an organic semiconductor layer including a compound of Formula (Ia), wherein the organic semiconductor layer is a hole injection layer; a light-emitting layer; and a cathode layer, wherein the hole injection layer and the light-emitting layer are disposed between the anode layer and the cathode layer, wherein the hole injection layer is disposed between the anode layer and the light-emitting layer, and wherein the hole injection layer is in direct contact with the anode layer.

[0349] According to one embodiment, an organic electroluminescent device includes: a substrate; an anode layer formed on the substrate; an organic semiconductor layer including a compound of Formula (Ia), wherein the organic semiconductor layer is a hole injection layer; a hole transport layer; a light-emitting layer; and a cathode layer, wherein the hole injection layer, the hole transport layer, and the light-emitting layer are disposed between the anode layer and the cathode layer, wherein the hole injection layer and the hole transport layer are disposed between the anode layer and the light-emitting layer, and wherein the hole injection layer is closer to the anode layer than the hole transport layer.

[0350] According to one embodiment, an organic electroluminescent device includes: a substrate; an anode layer formed on the substrate; an organic semiconductor layer including a compound of Formula (Ia), wherein the organic semiconductor layer is a hole injection layer; a hole transport layer; a light-emitting layer; and a cathode layer, wherein the hole injection layer, the hole transport layer, and the light-emitting layer are disposed between the anode layer and the cathode layer, wherein the hole injection layer and the hole transport layer are disposed between the anode layer and the light-emitting layer, wherein the hole injection layer is closer to the anode layer than the hole transport layer, wherein the hole injection layer is adjacent to the anode layer, and wherein the hole injection layer is adjacent to the hole transport layer.

[0351] According to one embodiment, an organic electroluminescent device includes: a substrate; an anode layer formed on the substrate; an organic semiconductor layer including a compound of Formula (Ia), wherein the organic semiconductor layer is a hole injection layer; a hole transport layer; a light-emitting layer; and a cathode layer, the hole injection layer and the hole transport layer are disposed between the anode layer and the light-emitting layer, wherein the hole injection layer and the hole transport layer are disposed between the anode layer and the light-emitting layer, wherein the hole injection layer is closer to the anode layer than the hole transport layer, wherein the hole injection layer is in direct contact with the anode layer, and wherein the hole injection layer is adjacent to the hole transport layer.

[0352] According to one embodiment, an organic electroluminescent device includes: a substrate; an anode layer formed on the substrate; an organic semiconductor layer including a compound of formula (Ia), wherein the organic semiconductor layer is a hole injection layer; a hole transport layer; a light-emitting layer; and a cathode layer, wherein the hole injection layer and the hole transport layer are disposed between the anode layer and the light-emitting layer, wherein the hole injection layer is closer to the anode layer than the hole transport layer, wherein the hole injection layer is in direct contact with the anode layer, and wherein the hole injection layer is in direct contact with the hole transport layer.

[0353] According to one embodiment, an organic electroluminescent device includes: a substrate; an anode layer formed on the substrate; an organic semiconductor layer including a compound of formula (Ia), wherein the organic semiconductor layer is a hole injection layer; a hole transport layer; an optional electron blocking layer; a light-emitting layer; an optional hole blocking layer; an electron transport layer; an optional electron injection layer; and a cathode layer.

[0354] According to one embodiment, an organic electroluminescent device includes: a substrate; an anode layer formed on the substrate; an organic semiconductor layer including a compound of formula (Ia), wherein the organic semiconductor layer is a hole injection layer, and wherein the hole injection layer is in direct contact with the anode layer; a hole transport layer; an optional electron blocking layer; a light-emitting layer; an optional hole blocking layer; an electron transport layer; an optional electron injection layer; and a cathode layer.

[0355] According to one embodiment, an organic electroluminescent device includes: a substrate; an anode layer formed on the substrate; an organic semiconductor layer including a compound of formula (Ia), wherein the organic semiconductor layer is a hole injection layer, and wherein the hole injection layer is in direct contact with the anode layer; a hole transport layer, wherein the hole transport layer is in direct contact with the hole injection layer; an optional electron blocking layer; a light-emitting layer; an optional hole blocking layer; an electron transport layer; an optional electron injection layer; and a cathode layer.

[0356] According to one embodiment, an organic electroluminescent device includes: a substrate; an anode layer formed on the substrate; an organic semiconductor layer including a compound of formula (Ia), wherein the organic semiconductor layer is a hole injection layer; a hole transport layer; an electron blocking layer; a light-emitting layer; an optional hole blocking layer; an electron transport layer; an optional electron injection layer; and a cathode layer.

[0357] According to one embodiment, an organic electroluminescent device includes: a substrate; an anode layer formed on the substrate; an organic semiconductor layer including a compound of formula (Ia), wherein the organic semiconductor layer is a hole injection layer, and wherein the hole injection layer is in direct contact with the anode layer; a hole transport layer; an electron blocking layer; a light-emitting layer; an optional hole blocking layer; an electron transport layer; an optional electron injection layer; and a cathode layer.

[0358] According to one embodiment, an organic electroluminescent device includes: a substrate; an anode layer formed on the substrate; an organic semiconductor layer including a compound of Formula (Ia), wherein the organic semiconductor layer is a hole injection layer, and the hole injection layer is in direct contact with the anode layer; a hole transport layer, wherein the hole transport layer is in direct contact with the hole injection layer; an electron blocking layer; a light emitting layer; an optional hole blocking layer; an electron transport layer; an optional electron injection layer; and a cathode layer.

[0359] According to one embodiment, an organic electroluminescent device includes: a substrate; an anode layer formed on the substrate; an organic semiconductor layer including a compound of Formula (Ia), wherein the organic semiconductor layer is a hole injection layer; a hole transport layer; an electron blocking layer; a light emitting layer; an optional hole blocking layer; an electron transport layer; an electron injection layer; and a cathode layer.

[0360] According to one embodiment, an organic electroluminescent device includes: a substrate; an anode layer formed on the substrate; a hole injection layer including a compound of Formula (Ia), the hole injection layer being in direct contact with the anode layer; a hole transport layer; an electron blocking layer; a light emitting layer; an optional hole blocking layer; an electron transport layer; an electron injection layer; and a cathode layer.

[0361] According to one embodiment, an organic electroluminescent device includes: a substrate; an anode layer formed on the substrate; a hole injection layer including a compound of Formula (Ia), the hole injection layer being in direct contact with the anode layer; a hole transport layer, wherein the hole transport layer is in direct contact with the hole injection layer; an electron blocking layer; a light emitting layer; an optional hole blocking layer; an electron transport layer; an electron injection layer; and a cathode layer.

[0362] According to one embodiment, an organic electroluminescent device includes: a substrate; an anode layer formed on the substrate; a hole injection layer including a compound of Formula (Ia); a hole transport layer; an electron blocking layer; a light emitting layer; a hole blocking layer; an electron transport layer; an electron injection layer; and a cathode layer.

[0363] According to one embodiment, an organic electroluminescent device includes: a substrate; an anode layer formed on the substrate; a hole injection layer including a compound of Formula (Ia), the hole injection layer being in direct contact with the anode layer; a hole transport layer; an electron blocking layer; a light emitting layer; a hole blocking layer; an electron transport layer; an electron injection layer; and a cathode layer.

[0364] According to one embodiment, an organic electroluminescent device includes: a substrate; an anode layer formed on the substrate; a hole injection layer including a compound of Formula (Ia); a hole transport layer; an electron blocking layer; a light emitting layer; a hole blocking layer; an electron transport layer; an electron injection layer; and a cathode layer.

[0365] According to one embodiment, an organic electroluminescent device includes: a substrate; an anode layer formed on the substrate; a hole injection layer including a compound of Formula (Ia), wherein the hole injection layer is in direct contact with the anode layer; a hole transport layer, wherein the hole transport layer is in direct contact with the hole injection layer; an electron blocking layer; a light emitting layer; a hole blocking layer; an electron transport layer; an electron injection layer; and a cathode layer.

[0366] According to one embodiment, an organic electroluminescent device includes: a substrate; an anode layer formed on the substrate; a hole injection layer including a compound of Formula (Ia), wherein the hole injection layer is in direct contact with the anode layer; a hole transport layer, wherein the hole transport layer is in direct contact with the hole injection layer; an electron blocking layer, wherein the electron blocking layer is in direct contact with the hole transport layer; a light emitting layer, wherein the light emitting layer is in direct contact with the electron blocking layer; a hole blocking layer, wherein the hole blocking layer is in direct contact with the light emitting layer; an electron transport layer, wherein the electron transport layer is in direct contact with the hole blocking layer; an electron injection layer, wherein the electron injection layer is in direct contact with the electron transport layer; and a cathode layer.

[0367] According to one embodiment, based on the total weight of the hole injection layer, the amount of the compound of Formula (Ia) present is ≤ 99.9 wt%, preferably ≤ 99 wt%, more preferably ≤ 95 wt%, more preferably ≤ 90 wt%, more preferably ≤ 80 wt%, more preferably ≤ 70 wt%, more preferably ≤ 60 wt%, more preferably ≤ 50 wt%, more preferably ≤ 40 wt%, more preferably ≤ 30 wt%, more preferably ≤ 20 wt%, more preferably ≤ 10 wt%, more preferably ≤ 5 wt%, more preferably ≤ 3.0 wt%, more preferably ≤ 2.75 wt%, more preferably ≤ 2.5 wt%, more preferably ≤ 2.25 wt%, and most preferably ≤ 2.0 wt%.

[0368] According to one embodiment, based on the total weight of the hole injection layer, the amount of the hole transport matrix compound present in the hole injection layer is ≥ 0.1 wt%, preferably ≥ 1 wt%, more preferably ≥ 5 wt%, more preferably ≥ 10 wt%, more preferably ≥ 20 wt%, more preferably ≥ 30 wt%, more preferably ≥ 40 wt%, more preferably ≥ 50 wt%, more preferably ≥ 60 wt%, more preferably ≥ 70 wt%, more preferably ≥ 80 wt%, more preferably ≥ 90 wt%, more preferably ≥ 95 wt%, more preferably ≥ 97.0 wt%, more preferably ≥ 97.25 wt%, more preferably ≥ 97.5 wt%, more preferably ≥ 97.75 wt%, and most preferably ≥ 98.0 wt%.

[0369] According to one embodiment, based on the total weight of the hole injection layer, the amount of the compound of formula (Ia) present is ≤99.9% by weight, preferably ≤99% by weight, more preferably ≤95% by weight, more preferably ≤90% by weight, more preferably ≤80% by weight, more preferably ≤70% by weight, more preferably ≤60% by weight, more preferably ≤50% by weight, more preferably ≤40% by weight, more preferably ≤30% by weight, more preferably ≤20% by weight, more preferably ≤10% by weight, more preferably ≤5% by weight, more preferably ≤3.0% by weight, more preferably ≤2.75% by weight, more preferably ≤2.5% by weight, more preferably ≤2.25% by weight, most preferably ≤2.0% by weight, and wherein based on the total weight of the hole injection layer, the amount of the hole transporting matrix compound present in the hole injection layer is ≥0.1% by weight, preferably ≥1% by weight, more preferably ≥5% by weight, more preferably ≥10% by weight, more preferably ≥20% by weight, more preferably ≥30% by weight, more preferably ≥40% by weight, more preferably ≥50% by weight, more preferably ≥60% by weight, more preferably ≥70% by weight, more preferably ≥80% by weight, more preferably ≥90% by weight, more preferably ≥95% by weight, more preferably ≥97.0% by weight, more preferably ≥97.25% by weight, more preferably ≥97.5% by weight, more preferably ≥97.75% by weight, most preferably ≥98.0% by weight.

[0370] According to one embodiment, the p-type charge generation layer comprising the compound of formula (Ia) further comprises a hole transporting matrix compound.

[0371] According to one embodiment, based on the total weight of the p-type charge generation layer, the amount of the compound of formula (Ia) present in the p-type charge generation layer is ≤99.9% by weight, preferably ≤99% by weight, more preferably ≤95% by weight, more preferably ≤90% by weight, more preferably ≤80% by weight, more preferably ≤70% by weight, more preferably ≤60% by weight, more preferably ≤50% by weight, more preferably ≤40% by weight, more preferably ≤30% by weight, more preferably ≤20% by weight, more preferably ≤10% by weight, more preferably ≤5% by weight.

[0372] According to one embodiment, based on the total weight of the p-type charge generation layer, the amount of the hole transporting matrix compound present in the p-type charge generation layer is ≥0.1% by weight, preferably ≥1% by weight, more preferably ≥5% by weight, more preferably ≥10% by weight, more preferably ≥20% by weight, more preferably ≥30% by weight, more preferably ≥40% by weight, more preferably ≥50% by weight, more preferably ≥60% by weight, more preferably ≥70% by weight, more preferably ≥80% by weight, more preferably ≥90% by weight, more preferably ≥95% by weight.

[0373] According to one embodiment, based on the total weight of the p-type charge generation layer, the amount of the compound of formula (Ia) present in the p-type charge generation layer is ≤ 99.9% by weight, preferably ≤ 99% by weight, more preferably ≤ 95% by weight, more preferably ≤ 90% by weight, more preferably ≤ 80% by weight, more preferably ≤ 70% by weight, more preferably ≤ 60% by weight, more preferably ≤ 50% by weight, more preferably ≤ 40% by weight, more preferably ≤ 30% by weight, more preferably ≤ 20% by weight, more preferably ≤ 10% by weight, more preferably ≤ 5% by weight, and based on the total weight of the p-type charge generation layer, the amount of the hole transport matrix compound present in the p-type charge generation layer is ≥ 0.1% by weight, preferably ≥ 1% by weight, more preferably ≥ 5% by weight, more preferably ≥ 10% by weight, more preferably ≥ 20% by weight, more preferably ≥ 30% by weight, more preferably ≥ 40% by weight, more preferably ≥ 50% by weight, more preferably ≥ 60% by weight, more preferably ≥ 70% by weight, more preferably ≥ 80% by weight, more preferably ≥ 90% by weight, more preferably ≥ 95% by weight.

[0374] The present invention also relates to an organic electroluminescent device including the organic semiconductor layer as described above and a display device including the organic electroluminescent device.

[0375] Hereinafter, the embodiments will be described in more detail with reference to examples. However, the present disclosure is not limited to the following examples. Now, exemplary aspects will be described in detail. BRIEF DESCRIPTION OF THE DRAWINGS

[0376] In the above-described embodiments, there are no special exceptions in terms of the size, shape, material selection, and technical concept of the above components, the claimed components, and the components used according to the present invention, so that the selection criteria known in the relevant art can be applied without limitation.

[0377] More details, features, and advantages of the object of the present invention are disclosed in the dependent claims and the following description of each drawing, which show exemplary embodiments according to the present invention. However, any embodiment does not necessarily represent the entire scope of the present invention, and thus the scope of the present invention is interpreted with reference to the claims and the present specification. It should be understood that the above general description and the following detailed description are both exemplary and explanatory, and are intended to provide further explanation of the claimed present invention.

[0378] Figure 1 is a schematic cross-sectional view of an OLED including a charge generation layer according to an exemplary embodiment of the present invention.

[0379] Figure 2 is a schematic cross-sectional view of an OLED including a charge generation layer according to an exemplary embodiment of the present invention.

[0380] Figure 3It is a schematic cross-sectional view of an OLED including a charge generation layer according to an exemplary embodiment of the present invention.

[0381] Figure 4 It is a schematic cross-sectional view of a stacked OLED including a charge generation layer according to an exemplary embodiment of the present invention.

[0382] The accompanying drawings will be described in more detail below with reference to examples. However, the present invention is not limited to the following drawings.

[0383] In this document, when a first element is referred to as being formed or disposed "on" or "above" a second element, the first element may be directly disposed on the second element, or one or more other elements may be disposed therebetween. When a first element is referred to as being "directly" formed or disposed "on" or "above" a second element, no other elements are disposed therebetween.

[0384] Figure 1 It is a schematic cross-sectional view of an OLED 100 according to the present invention.

[0385] Referring to Figure 1 , the OLED 100 includes an anode layer 120, a first emitting layer (EML1) 150, an n-type charge generation layer (n-CGL) 185, a p-type charge generation layer (p-GCL) 135 that may include a compound of formula (I), a second emitting layer (EML2) 151, and a cathode layer 190.

[0386] Figure 2 It is a schematic cross-sectional view of an OLED 100 according to the present invention.

[0387] Referring to Figure 2 , the OLED 100 includes an anode layer 120, a hole injection layer (HIL) 130, a first emitting layer (EML1) 150, an n-type charge generation layer (n-CGL) 185, a p-type charge generation layer (p-GCL) 135 that may include a compound of formula (I), a second emitting layer (EML2) 151, and a cathode layer 190.

[0388] Figure 3 It is a schematic cross-sectional view of an OLED 100 according to an exemplary embodiment of the present invention.

[0389] Referring to Figure 3, the OLED 100 includes: a substrate 110, an anode layer 120, a hole injection layer (HIL) 130, a first hole transport layer (HTL1) 140, an electron blocking layer (EBL) 145, a light emitting layer (EML) 150, a hole blocking layer (HBL) 155, an electron transport layer (ETL) 160, an n-type charge generation layer (n-CGL) 185, a p-type charge generation layer (p-GCL) 135 that may include a compound of formula (I), a second hole transport layer (HTL2) 141, an electron injection layer (EIL) 180, and a cathode layer 190. The HIL may include a compound of formula (I).

[0390] Figure 4 is a schematic cross-sectional view of a stacked OLED 100 according to another exemplary embodiment of the present invention.

[0391] Referring to Figure 4 , the OLED 100 includes: a substrate 110; an anode layer 120; a hole injection layer (HIL) 130; a first hole transport layer (HTL) 140; a first electron blocking layer (EBL) 145; a first light emitting layer (EML) 150; a first hole blocking layer (HBL) 155; a first electron transport layer (ETL) 160; an n-type charge generation layer (n-CGL) 185; a p-type charge generation layer (p-GCL) 135, which may include a compound of formula (I) or formula (Ia); a second hole transport layer (HTL) 141; a second electron blocking layer (EBL) 146; a second light emitting layer (EML) 151; a second hole blocking layer (EBL) 156; a second electron transport layer (ETL) 161; an electron injection layer (EIL) 180; and a cathode 190. The HIL may include a compound of formula (I) or formula (Ia), where the compound of formula (I) or formula (Ia) in the p-type charge generation layer and in the hole injection layer may be the same or different.

[0392] In the above description, the method of manufacturing the OLED 100 of the present invention starts from a substrate 110, forms an anode layer 120 on the substrate, and forms on the anode layer 120: a hole injection layer 130, which may contain a compound of formula (I) or formula (Ia); a first hole transport layer 140; an optional first electron blocking layer 145; a first light-emitting layer 150; an optional first hole blocking layer 155; an optional at least one first electron transport layer 160; an n-CGL 185; a p-CGL 135, which may contain a compound of formula (I) or formula (Ia); a second hole transport layer 141; an optional second electron blocking layer 146; a second light-emitting layer 151; an optional second hole blocking layer 156; an optional at least one second electron transport layer 161; an optional electron injection layer (EIL) 180; and a cathode layer 190, implemented in sequence or in the reverse order, wherein the compound of formula (I) or formula (Ia) in the p-type charge generation layer and in the hole injection layer may be the same or different.

[0393] Although not shown in Figures 1 to 4 , a sealing layer and / or a covering layer may be further formed on the cathode layer 190 to seal the organic electronic device 100. In addition, various other modifications can be made thereto.

[0394] Hereinafter, one or more exemplary embodiments of the present invention will be described in detail with reference to the following examples. However, these examples are not intended to limit the purpose and scope of one or more exemplary embodiments of the present invention. Detailed Description

[0395] The present invention is also illustrated by the following examples which are merely exemplary and not restrictive.

[0396] The compound of formula (I) and / or (Ia) can be prepared as described in EP 2180029 A1 and WO 2016097017A1.

[0397] The additional synthesis processes of the selected precursors for preparing the compounds according to the present invention are as follows in particular:

[0398] General synthetic route I:

[0399]

[0400] Intermediate 1a

[0401] Bromine (36 ml, 112 g, 1.42 mol) in dichloromethane (DCM) (250 ml) was added portionwise to a stirred solution of 3,5-bis(trifluoromethyl)aniline (50 g, 214 mmol), sodium carbonate (25 g, 235 mmol) and iron powder (500 mg, 9.0 mmol) in DCM (250 ml). The mixture was refluxed for 24 h. After cooling, DCM (250 ml) was added and the solution was washed with 10% Na2S2O3·5H2O (2 x 200 ml) and brine (200 ml), dried over MgSO4 and concentrated in vacuo to give the title compound as a pale yellow solid (75 g, 91%), which was purified by vacuum distillation or used in the next step without further purification.

[0402] Melting point 52 °C to 53 °C. Boiling point 105 °C / 1 mmHg.

[0403] Intermediate 2a

[0404] 2,6-Dibromo-3,5-bis(trifluoromethyl)aniline (20 g, 52 mmol) was added to copper(II) cyanide (20 g, 223 mmol) in N,N-dimethylformamide (DMF) (100 ml) and the mixture was heated at 160 °C for 12 h with stirring. After cooling, the reaction mixture was poured into saturated sodium carbonate solution (300 ml), the resulting precipitate was filtered and washed on the filter with ether (3 x 150 ml). The resulting aqueous-ether filtrate was extracted with a further amount of ether (3 x 150 ml), washed with brine (200 ml), dried over magnesium sulfate, filtered and evaporated. Dichloromethane was added to the residue to precipitate the product, which was then separated by filtration, giving solid 2 as a carrot-colored solid with a purity of 80%. For further purification, the solid was sublimed (160 °C / 1 mmHg).

[0405] Colorless solid. 156 °C to 158 °C.

[0406] Intermediate 3a

[0407] A three-necked round-bottom flask equipped with an addition funnel and a gas outlet tube and equipped with CuCl2 (3 g, 22 mmol) was flame dried in a vacuum and filled with argon (commercially available CuCl2, violent "boiling" releases water). A thermometer was installed and a stirring rod was lowered. 2-amino-4,6-bis(trifluoromethyl)isophthalonitrile 2 (4 g, 14 mmol) and acetonitrile (30 ml) were added. The obtained suspension was heated to 80 ° C under an argon atmosphere, and isoamyl nitrite (i-AmONO) (2.52 g, 3.0 ml, 22 mmol) was added dropwise within 3 minutes. The reaction mixture was heated at this temperature for 1.5 hours, then cooled to room temperature, poured into ether and washed with brine (3 times × 200 ml). The organic layer was dried over MgSO4, filtered, and evaporated. Column chromatography gave the product (2.5 g, 59%) in the form of colorless crystals.

[0408] Colorless crystals, melting point 117℃ to 119℃.

[0409] General synthetic route II:

[0410]

[0411] Intermediate 1b

[0412] To the solution of 88.1g of perfluoro-p-xylene and 34.8g of ethyl cyanoacetate in 500mlDMF, 51.1g of potassium carbonate was added, and the resulting suspension was stirred at room temperature for 44 hours. After the reaction was completed, the mixture was poured on an ice / water mixture and acidified with hydrochloric acid. The aqueous phase was extracted 2 times with DCM. The organic layer merged was washed with salt water, dried over sodium sulfate and evaporated solvent. The resulting yellow oil was used for the next step without further purification.

[0413] Intermediate 2b

[0414] Intermediate 1b is suspended in a mixture of 12.7 ml sulfuric acid, 480 ml 50% acetic acid. The mixture is stirred at 100 ° C for 113 hours. After cooling to room temperature, the two layers are separated. The aqueous phase is diluted with ice water and extracted with DCM. The combined organic layers are neutralized by washing with a bicarbonate solution, then washed with brine and dried over sodium sulfate. After evaporation of the organic solvent, the crude product is purified by filtration through a silica pad using hexane / ethyl acetate 6:4 (yield: 60%; 56.6 g).

[0415] Intermediate 3b

[0416] The apparatus containing 24.9 g of Intermediate 2b in 600 ml of anhydrous dimethyl sulfoxide (DMSO) was flushed with an inert gas and cooled to 20 °C with cold water. Sodium borohydride (3.2 g; 1 equivalent) was added within 15 minutes. After stirring for an additional 15 minutes, the starting material was consumed, and the reaction mixture was poured into a mixture of 350 ml of brine and 1000 ml of ethyl acetate and stirred for 5 minutes. The organic phase was separated, concentrated to approximately 500 ml. The concentrated solution was washed with brine, dried over sodium sulfate and further concentrated to give a red oil, which was purified by column chromatography (volume: volume ethyl acetate 8:2, yield: 40%, 13 g).

[0417] Reagents 1-2

[0418] Intermediate 3b (21.1 g), potassium cyanide (14.3 g, 3 equivalents) and 18-crown-6-ether (57.8 g, 3 equivalents) were suspended in 280 ml of anhydrous tetrahydrofuran (THF). The mixture was stirred at 50 °C for 4 hours. After cooling to room temperature, the organic phase was washed with saturated sodium bicarbonate solution, filtered through a silica pad using DCM as the eluent, and the solvent was evaporated. After recrystallization from 15 ml of isopropanol, the product was obtained in 38% yield (8.36 g).

[0419] General synthetic route III:

[0420]

[0421] Intermediate 4

[0422] To a solution of 1 g of aryl halide (Intermediate 3) dissolved in 10 mL of DMF was added 1.2 equivalents of potassium carbonate. After dropwise addition of 1.2 equivalents of ethyl cyanoacetate or tert-butyl cyanoacetate, the mixture was stirred at 50 °C for 3 days. The solid by-products were removed by filtration and the filtrate was evaporated to dryness. The crude product was triturated with DCM (2 hours, room temperature) twice, the precipitated product was collected on a frit and washed three times with DCM. The final product was dried under vacuum overnight.

[0423] Reagent 1 (Method a: R = ethyl)

[0424] To a solution of 1 g of Intermediate 4 in 3 mL of acetic acid (50%) was added 1.5 equivalents of concentrated sulfuric acid. The mixture was heated to reflux (130 °C bath temperature) for 1 to 3 days. After cooling to room temperature, the mixture was poured into 10 mL of ice water and stirred for a period of 30 minutes, followed by the addition of 10 mL of ethyl acetate. The aqueous phase was separated and washed three times with ethyl acetate. The combined organic phases were dried over sodium sulfate and the solvent was evaporated to dryness. The crude product was dried under vacuum at ambient temperature overnight and purified by vacuum distillation.

[0425] Reagent 1 (Method b: R = ethyl)

[0426] Dissolve 1 g of Intermediate 4 in 10 mL of water and triturate with acetic acid until the pH of the solution is 3. After adding 5 mL of ethyl acetate, extract the aqueous phase twice with 5 mL of ethyl acetate. After drying the combined organic phases over sodium sulfate, evaporate the solvent to dryness. Dissolve the remaining oil in 10 mL of DMSO under an inert gas atmosphere and add 5 mL of brine. Stir the mixture under gentle reflux for 3 to 24 hours. After cooling to room temperature, add 15 mL of water and 25 mL of ethyl acetate. Separate the aqueous phase and wash it twice with ethyl acetate. After extracting twice with brine and drying the combined organic phases over sodium sulfate, evaporate the solvent to dryness. Dry the crude product under vacuum at ambient temperature overnight and purify it by vacuum distillation.

[0427] Reagent 1 (Method c: R = tert-butyl)

[0428] Dissolve 5 g of Intermediate 4 in 10 mL of di ane in a pressure tube and add 2 equivalents of a 4 M solution of hydrogen chloride in di ane. Seal the tube and stir at 95 °C for 2 to 4 hours. After cooling to room temperature, pour the mixture onto 40 mL of water and extract three times with 30 mL of ethyl acetate. Wash the combined organic phases with 50 mL of water, 50 mL of 0.5 M sodium bicarbonate solution, and 50 mL of brine. After drying over sodium sulfate and evaporating the solvent, purify the compound by Kugelrohr distillation at 100 °C to 150 °C and 10 -3 mbar to obtain the final product.

[0429] Intermediate 5

[0430] Suspend 2.33 equivalents of sodium hydride in 14 mL of anhydrous dimethoxyethane (DME) in a dry Schlenk flask and cool to -10 °C. Dissolve 1 g of Reagent 1 in 2 mL of anhydrous DME and add dropwise to the suspension (exothermic; evolution of H2!). After complete addition, remove the cooling device and stir the mixture at ambient temperature for 1 hour while observing a slow color change. Cool the mixture to -10 °C and add dropwise a solution of 0.33 equivalents of 1,1,2,2,3-pentachlorocyclopropane (PCCP) (Reagent 2) in 1 mL of anhydrous DME (exothermic!). Then allow the mixture to warm to room temperature overnight and quench by dropwise addition of 20 mL of a saturated aqueous calcium chloride solution. Add 10 mL of deionized water and 20 mL of tert-butyl acetate to the resulting solution. Stir the mixture for 1 hour. Subsequently, separate the layers and wash the organic phase three times with 20 mL of water. Dry the organic layer over sodium sulfate and evaporate the solvent to obtain a black brittle foam. Use the intermediate without further purification.

[0431] Compound Ib / c

[0432] Dissolve intermediate 5 (1 g) in glacial acetic acid (10 mL), and dropwise add it to an aqueous nitric acid solution (65% weight / weight, 13 mL and 3 mL acetic acid) with stirring at 0 °C. The solution changes from black / green to red / orange. After stirring at 0 °C for 30 minutes, the solution is warmed to room temperature and stirred for an additional 1 hour to 4 hours. The crude product is precipitated by adding 10 mL of water, and the mixture is stirred for 15 minutes. The orange solid is filtered off and washed with cold water until the filtrate is neutral.

[0433] Workup and purification of I b / c

[0434] Dissolve the crude product in DCM and wash it twice with water to remove the remaining acid. In some cases, the product part is insoluble in DCM. The insoluble part filtered out has satisfactory purity and is to be sublimated.

[0435] The soluble part is concentrated by evaporation and precipitated from an excess of cyclohexane, filtered on a frit, and dried under high vacuum of an oil pump.

[0436] HOMO and LUMO calculations

[0437] Using the program packages ORCA V5.0.3 (Max Planck Institute für Kohlenforschung, KaiserWilhelm Platz 1, 45470, Muelheim / Ruhr, Germany) and WEASEL 1.9.2 (FAccTs GmbH, Rolandstrasse 67, 50677 Germany), calculate the HOMO and LUMO. Determine the dipole moment, HOMO, and LUMO energy levels of the molecular structure from the optimized geometric configuration obtained by applying the hybrid functional B3LYP with the 6-31G* basis set in the gas phase. All calculations are carried out in the gas phase. If more than one conformation is feasible, select the conformation with the lowest total energy.

[0438] Glass transition temperature

[0439] As described in DIN EN ISO 11357 published in March 2010, the glass transition temperature (Tg) is measured in a Mettler Toledo DSC 822e differential scanning calorimeter under nitrogen using a heating rate of 10 K per minute.

[0440] Melting point (mp)

[0441] The melting point (mp) temperature was measured by DSC at a heating rate of 10 K per minute, and the reported value corresponds to the peak temperature of the endothermic melting observed on the DSC curve.

[0442] Thermogravimetric analysis

[0443] The term “TGA 5%” refers to the temperature at which 5% weight loss occurs during thermogravimetric analysis and is measured in °C.

[0444] The TGA 5% value can be determined by heating a 9 mg to 11 mg sample in a thermogravimetric analyzer in an open 100 μL aluminum pan under a nitrogen flow of 20 mL per minute in the balance region and 30 mL per minute in the oven region at a heating rate of 10 K per minute.

[0445] The TGA 5% value can provide an indirect measure of the volatility and / or decomposition temperature of a compound. In a first approximation, the higher the TGA 5% value, the lower the volatility and / or the higher the decomposition temperature of the compound.

[0446] Measurement of UV-visible absorption in solution

[0447] The experimental absorption spectra were recorded on a Thermo Fisher Evolution Pro UV-Vis spectrophotometer. For sample preparation, the material was weighed into an aluminum crucible and then placed into a 25 mL volumetric flask. The mass change readability of the relevant microbalance was in the range of 1 μg to 2 μg. The volumetric flask was then filled to the mark with dichloromethane (spectral grade, transmittance ≥ 90% at λ ≥ 248 nm according to the manufacturer's instructions), and shaken until the material was completely dissolved, resulting in a solution with a concentration of 10 -4 mol / L to 10 -5 mol / L. For the measurement, the solution was placed into a standard cuvette (Hellma 110-QS: quartz, d = 10 mm, with PTFE stopper). At an ambient temperature of 20 °C, the spectra were recorded with a slit width of 1 nm and a sampling interval of 1 nm. The background absorption of the pure solvent, which was measured immediately before the measurement using the same measurement conditions, was subtracted from all spectra.

[0448] Measurement of light absorption rate of organic semiconductor layer

[0449] In a vacuum system (Cluster Tool, Sunic System Ltd.) at At a deposition rate of and a pressure of about 3e-7 mbar, a mixed film of N-([1,1'-biphenyl]-2-yl)-N-(9,9-dimethyl-9H-fluoren-2-yl)-9,9'-spirobi[fluorene]-2-amine and a p-type dopant (10 vol% p-type dopant) with a thickness of 35 nm was prepared on a quartz substrate (EN08, ≥99.98% SiO2, GVB GmbH) by thermal evaporation according to Table 2. The samples were stored in a glove box under a pure nitrogen atmosphere until measurement (air exposure up to 1 hour). Reflectance and transmittance were measured using a Filmetrics F10-RT spectrometer in the spectral range from 380 nm to 1050 nm. An empty quartz substrate was used as the reflectance standard. The absorbance was automatically calculated by subtracting the reflectance and transmittance values from 100%.

[0450] Calculated absorption area or maximum absorption

[0451] All calculations were performed using the ORCA package version 5.0.3 (Department of theory and spectroscopy, Max Planck Institute für Kohlenforschung Kaiser Wilhelm Platz 1, 45470 Muelheim / Ruhr, Germany).

[0452] The LUMO and HOMO energies and the resulting HOMO-LUMO energy gap were calculated in the gas phase using the hybrid functional B3LYP and the 6-31G* basis set. The hybrid functional PBE0 and the def2-SVP basis set were applied in the gas phase using the optimized geometries obtained thereby and including the first 30 singlet transitions to run TDDFT calculations. The calculated singlet transitions were used to calculate the absorption spectrum by applying a Gaussian fit (λ = 215 nm to 850 nm, SD = 20, 200 sampling points), excluding transitions below 350 nm.

[0453] To calculate the overall absorption in the relevant wavelength region (λ = 400 nm to 650 nm, blue and green emission), the integral under the calculated UV TDDFT spectrum was determined.

[0454] Calculated bond dissociation energy (BDE)

[0455] All calculations were carried out using the ORCA program package Version 5.0.3 (Department of theory and spectroscopy, Max Planck Institute für Kohlenforschung Kaiser Wilhelm Platz 1, 45470 Muelheim / Ruhr, Germany).

[0456] The homolytic bond dissociation energy (BDE), which is the energy required to dissociate one mole of covalently bonded gas into radical pairs, was calculated according to the reported procedure (J. Phys. Chem. A, 1999, 103, 11, 1653 - 1661).

[0457] The molecular geometries were optimized in the gas phase using the DFT functional BP86 and the Def2 - SVP basis set. If more than one conformation was available, the conformation with lower energy was selected. The optimized geometries were confirmed as minima by frequency analysis.

[0458] From the optimized geometries, ΔG (BP86 / Def2SVP) and the electronic energy (BP86 / D ef 2SVP) were obtained at the same geometric level. In the second calculation, the electronic energy (B3LYP / Def2TZVP) was obtained by single - point calculations in the gas phase using the DFT functional B3LYP and the Def2 - TZVP basis set.

[0459] The energy correction value was obtained as follows:

[0460] (ΔG (BP86 / Def2SVP) - electronic energy (BP86 / Def2SVP) ) + electronic energy (B3LYP / D ef 2TZVP) .

[0461] General procedure for manufacturing OLED

[0462] For the present invention, the following setup of an OLED with a hole - injection layer and a light - emitting layer can be used.

[0463] A glass substrate with an anode layer having a first anode sub - layer containing 120 nm Ag, a second anode sub - layer of 8 nm ITO, and a third anode sub - layer of 10 nm ITO was cut into a size of 50 mm×50 mm×0.7 mm, ultrasonically washed with water for 60 minutes, and then ultrasonically washed with isopropanol for 20 minutes. The liquid film was removed in a nitrogen stream, followed by plasma treatment, as shown in Table 2, to prepare the anode layer. The plasma treatment was carried out in an atmosphere containing 97.6 vol% nitrogen and 2.4 vol% oxygen.

[0464] Then, N-([1,1'-biphenyl]-4-yl)-N-(2-(9,9-diphenyl-9H-fluoren-4-yl)phenyl)-9,9-dimethyl-9H-fluoren-2-amine [1792219-00-1] and 20 vol% of the compound of formula (I) according to Table 4 or a comparative compound were vacuum deposited on the anode to form a HIL with a thickness of 10 nm.

[0465] Then, N-([1,1'-biphenyl]-4-yl)-N-(2-(9,9-diphenyl-9H-fluoren-4-yl)phenyl)-9,9-dimethyl-9H-fluoren-2-amine [1792219-00-1] was vacuum deposited on the HIL to form a first HTL with a thickness of 128 nm.

[0466] Then, N,N-bis([1,1'-biphenyl]-4-yl)-3'-(9H-carbazol-9-yl)-[1,1'-biphenyl]-4-amine [1464822-27-2] was vacuum deposited on the HTL to form an electron blocking layer (EBL) with a thickness of 5 nm.

[0467] Then, a first emitting layer (EML1) with a thickness of 20 nm was formed by co-depositing 99 vol% of dibenzofuran, 7-(phenyl-2,3,4,5,6-d)-1-[10-(phenyl-2,3,4,5,6-d)-9-anthryl] [2457172-82-4] as the EML host and 1 vol% of 5H,9H-[1]benzothieno[2',3':5,6][1,4]azaborinine borane, 2,7,11-tris(1,1-dimethylethyl)-5,9-bis[4-(1,1-dimethylethyl)phenyl] [2482607-57-6] as the blue dopant on the EBL1.

[0468] Then, a hole blocking layer with a thickness of 5 nm was formed by depositing 22-(3'-(9,9-dimethyl-9H-fluoren-2-yl)-[1,1'-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine [1955543-57-3] on the emitting layer.

[0469] Then, an electron transport layer (ETL) with a thickness of 31 nm was formed by depositing 50 wt% of 2-(2',6'-diphenyl-[1,1':4',1”-terphenyl]-4-yl)-4-phenyl-6-(3-(pyridin-4-yl)phenyl)-1,3,5-triazine [2869796-06-3] and 50 wt% of LiQ on the hole blocking layer.

[0470] Then, at 10 -7 mbar at to Evaporate Yb at a rate to form an electron injection layer with a thickness of 2 nm on the electron transport layer.

[0471] At 10 -7 mbar, evaporate Ag / Mg (90:10 vol%) at a rate of to to form a cathode with a thickness of 13 nm.

[0472] Then, vacuum deposit N-({[1,1'-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluoren-2-amine} on the cathode layer to form a capping layer with a thickness of 75 nm.

[0473] Protect the OLED stack from environmental conditions by encapsulating the device with a glass slide. Thereby, a cavity containing a getter material for further protection is formed.

[0474] Preparation of an OLED device containing a p-type charge generation layer comprising the compound of the present invention

[0475] For the examples and comparative examples according to the present invention in Table 3, a 15 Ω / cm glass substrate (available from Corning Co.) with 90 nm ITO is cut into a size of 50 mm × 50 mm × 0.7 mm, ultrasonically washed with isopropyl alcohol for 5 minutes, then ultrasonically washed with pure water for 5 minutes, and further washed with ultraviolet ozone for 30 minutes to prepare the anode. 2 Then, vacuum deposit N-([1,1'-biphenyl]-4-yl)-N-(2-(9,9-diphenyl-9H-fluoren-4-yl)phenyl)-9,9-dimethyl-9H-fluoren-2-amine together with 20 vol% of the compound according to Table 3 to form a hole injection layer (p-HIL) with a thickness of 10 nm.

[0476] Then, vacuum deposit N-([1,1'-biphenyl]-4-yl)-N-(2-(9,9-diphenyl-9H-fluoren-4-yl)phenyl)-9,9-dimethyl-9H-fluoren-2-amine to form a first hole transport layer with a thickness of 130 nm.

[0477] Then, vacuum deposit N,N-bis(4-(dibenz[b,d]furan-4-yl)phenyl)-[1,1':4',1”-terphenyl]-4-amine on the HTL to form an electron blocking layer (EBL) with a thickness of 5 nm.

[0478] Then, vacuum deposit N,N-bis(4-(dibenz[b,d]furan-4-yl)phenyl)-[1,1':4',1”-terphenyl]-4-amine on the HTL to form an electron blocking layer (EBL) with a thickness of 5 nm.

[0479] Then, 97 wt% of H09 (Sun Fine Chemicals, Korea) as the EML host and 3 wt% of BD200 (Sun Fine Chemicals, Korea) as the fluorescent blue dopant were deposited on the EBL to form a first blue-emitting emissive layer (EML) with a thickness of 20 nm.

[0480] Then, a first hole blocking layer (HBL1) with a thickness of 25 nm was formed by depositing 2-(3'-(9,9-dimethyl-9H-fluoren-2-yl)-[1,1'-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine on the first emissive layer.

[0481] Then, an n-type CGL (n-type charge generation layer) with a thickness of 15 nm was formed by co-depositing 99 vol% of 3-phenyl-3H-benzo[b]dinaphtho[2,1-d:1',2'-f][1,2,5]oxadiazole and 1 vol% of Yb on the first hole blocking layer (HBL1).

[0482] Then, a p-type CGL with a thickness of 10 nm was formed by co-depositing N-([1,1'-biphenyl]-4-yl)-N-(2-(9,9-diphenyl-9H-fluoren-4-yl)phenyl)-9,9-dimethyl-9H-fluoren-2-amine with 20 vol% of the compound according to Table 3 on the n-type CGL.

[0483] Then, a second hole transport layer with a thickness of 21 nm was formed by depositing N-([1,1'-biphenyl]-4-yl)-N-(2-(9,9-diphenyl-9H-fluoren-4-yl)phenyl)-9,9-dimethyl-9H-fluoren-2-amine on the first p-type CGL.

[0484] Then, a second electron blocking layer with a thickness of 5 nm was formed by depositing N,N-bis(4-(dibenzo[b,d]furan-4-yl)phenyl)-[1,1':4',1''-terphenyl]-4-amine on the second hole transport layer.

[0485] Then, 97 wt% of H09 (Sun Fine Chemicals, Korea) as the EML host and 3 wt% of BD200 (Sun Fine Chemicals, Korea) as the fluorescent blue dopant were deposited on the second EBL to form a second blue-emitting EML with a thickness of 20 nm.

[0486] Then, 2-(3'-(9,9-dimethyl-9H-fluoren-2-yl)-[1,1'-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine was vacuum deposited to form a second hole blocking layer with a thickness of 10 nm on the second blue-emitting EML.

[0487] Then, 50 wt% of 4'-(4-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)naphthalen-1-yl)-[1,1'-biphenyl]-4-carbonitrile and 50 wt% of LiQ were vacuum deposited on the second hole blocking layer to form a second electron transport layer with a thickness of 25 nm.

[0488] At 10 -7 mbar, Al was evaporated at a rate to form a cathode with a thickness of 100 nm.

[0489] To evaluate the performance of the examples of the present invention compared to the prior art, the current efficiency was measured at 20 °C. Using a Keithley 2635 source measurement unit, the current-voltage characteristics were determined by providing a voltage in volts and measuring the current in milliamperes flowing through the device under test. The voltage applied to the device was varied in steps of 0.1 V in the range between 0 V and 10 V. Similarly, the luminance-voltage characteristics and CIE coordinates were determined by measuring the luminance in cd / m 2 at each voltage value using an Instrument Systems CAS-140CT array spectrometer (calibrated by Deutsche Akkreditierungsstelle (DAkkS)). The cd / A efficiency at 10 mA / cm 2 was determined by interpolating the luminance-voltage and current-voltage characteristics, respectively.

[0490] In bottom-emitting devices, the emission is mainly of the Lambertian type and is quantified as a percentage of the external quantum efficiency (EQE). To determine the efficiency EQE in %, the light output of the device was measured at 10 mA / cm 2 using a calibrated photodiode.

[0491] In top-emitting devices, the emission is forward, non-Lambertian, and also highly dependent on the microcavity. Therefore, the efficiency EQE will be higher compared to bottom-emitting devices. To determine the efficiency EQE in %, the light output of the device was measured at 10 mA / cm 2 using a calibrated photodiode.

[0492] At room temperature (20 °C) or 60 °C and 30 mA / cm 2Under this condition, a Keithley 2400 source meter is used to measure the lifetime LT of the device and record it in hours.

[0493] The brightness of the device is measured using a calibrated photodiode. The lifetime LT is defined as the time until the brightness of the device drops to 97% of its initial value.

[0494] The increment ΔV of the operating voltage is used as a measure of the operating voltage stability of the device. This increment is determined by subtracting the operating voltage 1 hour after the device starts operating from the operating voltage 100 hours later during the LT measurement.

[0495] ΔV = [V(100h) - V(1h)].

[0496] The smaller the value of ΔV, the better the operating voltage stability.

[0497] Luminous flux

[0498] The sample is placed separately in an integrating sphere, and the luminous flux with a hemispherical lens (HSL) and without a hemispherical lens (HSL) is measured using an Instrument Systems CAS-140CT array spectrometer (calibrated by Deutsche Akkreditierungsstelle (DAkkS)) at a current density of 10 mA / cm 2 As a constant current source, a Keithley 2635 source measurement unit is used.

[0499] Table 1a shows the structures; Table 1b shows the properties of the comparative compounds; Table 1c shows the properties of the selected compounds (HOMO and E-Gap, i.e., the difference between HOMO and LUMO):

[0500] For Table 1a, the following core structures are used:

[0501]

[0502] Table 1a: Structures of the selected compounds

[0503]

[0504] Table 1b: Properties of the selected compounds

[0505]

[0506] Table 1c: Structures and properties of the selected compounds

[0507]

[0508]

[0509]

[0510] The compounds, especially the compounds of the present invention, exhibit a high Egap (the energy difference between the HOMO level and the LUMO level), and thus have low absorption in the range of 300 nm to 650 nm.

[0511] Therefore, the compounds can be beneficial for providing organic electronic devices or display devices with increased display brightness. If a lower current density is used, the lifespan of the display can be extended.

[0512] In addition, the compounds can be beneficial for providing organic electronic devices or display devices with improved efficiencies such as external quantum efficiency and current efficiency.

[0513] Table 2: Light absorption rate of the p-type charge generation layer (solid film)

[0514]

[0515] * = a.u.x nm of the solid film

[0516] As can be seen from Table 2, compounds containing an axylene such as B1 and B2 with an Egap (the energy difference between the HOMO level and the LUMO level) greater than that of the comparative compounds CE1 to CE-2 exhibit a lower λabs(max), and the layer containing the axylene and the organic hole transport compound exhibits lower visible light absorption than the comparative compounds CE1 to CE-2 and the organic hole transport compound, especially for the green and blue parts of the visible light.

[0517] This can be beneficial for increasing the brightness of the display. If a lower current density is used, the lifespan of the display can be extended.

[0518] In addition, the compounds can be beneficial for providing organic electronic devices or display devices with improved efficiencies such as external quantum efficiency and current efficiency.

[0519] Table 3 shows the properties and comparative data of selected devices in the stacked OLEDs containing p-CGL according to the present invention, and Table 4 shows the properties and comparative data of selected devices in the single-unit OLEDs according to the present invention:

[0520] Table 3:

[0521]

[0522] Table 4:

[0523]

[0524] The devices Inv-1 and Inv-2 of the present invention exhibit good operating voltages and voltage rises (ΔV) lower than those of the comparative devices C-1 and C-2.

[0525] Compared with the comparative compounds CE-1 and CE-2 containing aryl moieties with direct fluorine bonding in the p-type charge generation layers for the comparative devices C-1 and C-2, when used in the p-type charge generation layers of the devices Inv-1 and Inv-2 of the present invention, the compounds B1 and B2 without direct fluorine bonding in the aryl moieties can exhibit lower voltage rises over time (Table 3).

[0526] A low voltage rise over time can lead to an improvement in the long-term stability of organic electronic devices.

[0527] In addition, when using the compound or the organic electronic device (Inv-1) according to the present invention, a higher light flux can be measured. The organic electronic device (Inv-1 or Inv-2) according to the present invention contains a compound of formula (I) or (Ia), and its E-Gap (the difference between the HOMO level and the LUMO level) is higher than that of the compound CE-1 or CE-2 used in the comparative device C-1 or C-2, respectively. This can be beneficial for increasing the brightness of the display, or when using a lower current density, it can extend the life of the display. In addition, when using the compound or the organic electronic device according to the present invention, higher efficiencies such as external quantum efficiency and current efficiency can be measured. The organic electronic device (Inv-1) according to the present invention contains a compound of formula (I) or (Ia), and its E-Gap (the difference between the HOMO level and the LUMO level) is higher than that of the compound CE-1 or CE-2 used in the comparative device C-1 or C-2, respectively. High efficiency can be beneficial for reducing power consumption and improving battery life, especially in mobile devices.

[0528] When using the compound or the organic electronic device according to the present invention, higher efficiencies such as external quantum efficiency and current efficiency can be measured (see Table 4). The organic electronic devices (Inv-1 and Inv-2) according to the present invention contain a compound of formula (I) or (Ia), and its E-Gap (the difference between the HOMO level and the LUMO level) is higher than that of the compound CE-1 or CE-2 used in the comparative device C-1 or C-2, respectively. High efficiency can be beneficial for reducing power consumption and improving battery life, especially in mobile devices.

[0529] In addition, the TGA5% values of several compounds were measured, and the results are shown in Table 5:

[0530] Table 5: TGA5% values of selected compounds

[0531] Name TGA5% [°C] Comparison CE-3 264 Invention B1 409 Invention B2 334

[0532] Obviously, the compounds of the present invention exhibit a TGA5% higher than that of the comparative compounds.

[0533] Since the TGA5% value can be regarded as an indirect measure of the volatility and / or decomposition temperature of the compound. In a first approximation, the higher the TGA5% value, the lower the volatility and / or the higher the decomposition temperature of the compound. Therefore, the compounds of the present invention exhibit lower volatility and higher thermal stability, i.e., have a higher decomposition temperature.

[0534] The higher TGA5% (lower volatility) can be beneficial for better control of the processing of organic electronic devices through a thermal evaporation process, especially in large-scale production, while the LUMO energy level and thus the doping intensity remain almost unchanged or are higher.

[0535] The specific combinations of elements and features in the above detailed embodiments are merely exemplary; exchanges and permutations of these teachings with other teachings in the patent applications incorporated herein and by reference are also expressly contemplated. As those skilled in the art will recognize, those skilled in the art can conceive of variations, modifications, and other embodiments described herein without departing from the spirit and scope of the claimed invention. Therefore, the above description is only an example and is not intended to be limiting. In the claims, the word "comprising" does not exclude other elements or steps, and the singular forms "a" or "an" do not exclude a plurality of referents. The fact that specific measures are recited in mutually different dependent claims does not indicate that a combination of these measures cannot be used advantageously. The scope of the present invention is defined by the claims and their equivalents. In addition, the reference numerals used in the description and claims do not limit the scope of the claimed invention.

Claims

1. An organic electroluminescent device, which comprises an anode layer, a cathode layer, a first light-emitting layer, a second light-emitting layer, and a charge generation layer, wherein the charge generation layer is disposed between the first light-emitting layer and the second light-emitting layer; wherein the charge generation layer comprises an n-type charge generation layer and a p-type charge generation layer; wherein the n-type charge generation layer is closer to the anode layer than the p-type charge generation layer; wherein the p-type charge generation layer comprises a compound of formula (I) wherein in formula (I), A is selected from formula (II) wherein R 1 to R 5 are independently selected from H, D, CN, CF3, a partially or fully perfluorinated C1 to C8 alkyl group, R 1 or R 5 at least one of which is selected from CN, CF3, a partially or fully perfluorinated C1-C8 alkyl group, R 1 to R 5 at least three of which are selected from CN, CF3, partially or fully perfluorinated C1-C8 alkyl groups wherein "*" represents the bonding position; and wherein A is not selected from:

2. The organic electroluminescent device according to claim 1, wherein in formula (II), R 1 to R 5 at least one of which is selected from CN.

3. The organic electroluminescent device according to any one of claims 1 or 2, wherein in formula (II), R 1 to R 5 at least three of which are selected from CN and CF3.

4. The organic electroluminescent device according to any one of claims 1 to 3, wherein in formula (II), R 1 to R 5 are four selected from CN, CF3, partially or completely perfluorinated C1 to C8 alkyl groups, and the rest are H or D.

5. The organic electroluminescent device according to any one of claims 1 to 4, wherein in formula (II), two of R 1 to R 5 are selected from CN.

6. The organic electroluminescent device according to any one of claims 1 to 5, wherein R 1 and R 5 are not both CF3.

7. The organic electroluminescent device according to any one of claims 1 to 6, wherein in formula (II), R k and R k+1 are each independently selected from H or D, where k is from 1 to 4.

8. The organic electroluminescent device according to any one of claims 1 to 7, wherein the compound of formula (I) has a molecular weight of ≤ 1250 g / mol, preferably ≤ 1100 g / mol, more preferably ≤ 1070 g / mol.

9. The organic electroluminescent device according to any one of claims 1 to 8, wherein the compound of formula (I) has a LUMO energy level, and the LUMO energy level of the compound of formula (Ia) or (IIa) is ≤ -4.65 eV, preferably ≤ -4.80 eV, more preferably ≤ -4.90 eV, more preferably ≤ -5.00 eV, more preferably ≤ -5.05 eV, more preferably ≤ -5.10 eV, and most preferably ≤ -5.15 eV.

10. The organic electroluminescent device according to any one of claims 1 to 9, wherein the compound of formula (I) has a LUMO energy level and a HOMO energy level, and the difference between the LUMO energy level and the HOMO energy level is ≥ 2.75 eV, preferably ≥ 2.80 eV, more preferably ≥ 2.85 eV, more preferably ≥ 2.90 eV, and most preferably ≥ 2.94 eV.

11. The organic electroluminescent device according to any one of claims 1 to 10, wherein the compound of formula (I) has C3-symmetry.

12. A compound according to formula (Ia) wherein in formula (Ia), A 1 is selected from the group of formula (IIa) wherein R 1 to R 5 are independently selected from H, D, CN, CF3 or a partially or fully perfluorinated C1 to C8 alkyl group, R 1 or R 5 at least one of which is selected from CN, CF3 or a partially or fully perfluorinated C1-C8 alkyl group, R 1 to R 5 at least three of which are selected from CN, CF3 or a partially or fully perfluorinated C1 to C8 alkyl group, R 1 to R 5 at least one of which is selected from CN, and R 1 to R 5 at least one of which is selected from CF3 or a partially or fully fluorinated C1-C8 alkyl group, wherein "*" represents the bonding position; Among which, A below is excluded 1 Part 13. An organic semiconductor layer, which comprises the compound according to claim 12.

14. An organic electroluminescent device, which comprises the organic semiconductor layer according to claim 13.

15. A display device, which comprises the organic electroluminescent device according to any one of claims 1 to 11 or 14.

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