Organic compound, mixture, composition and application of organic compound, mixture and composition in organic electronic device

Abstract

The invention discloses an organic compound, a mixture, a composition and an application of the organic compound, the mixture and the composition in an organic electronic device, especially an application in an organic light-emitting diode. The invention also discloses an organic electronic device comprising the organic compound according to the invention, especially an organic electroluminescent diode, and application of the organic electronic device in display and illumination technologies. Through device structure optimization, better device performance can be achieved, especially a high-performance OLED device can be realized, and better material and preparation technology options are provided for full-color display and illumination application.

Description

Technical Field

[0001] The present invention relates to the field of electroluminescent materials, and in particular to an organic compound, a polymer, a mixture and a composition thereof, and applications thereof in organic electronic devices, in particular in electroluminescent devices. Background Art

[0002] Organic semiconductor materials have great potential for application in optoelectronic devices such as organic light-emitting diodes (OLEDs), such as flat-panel displays and lighting, due to their structural diversity, relatively low manufacturing costs, and superior optoelectronic properties.

[0003] Organic electroluminescence refers to the phenomenon of converting electrical energy into light energy using organic substances. Organic electroluminescent elements that use organic electroluminescence usually have an anode and a cathode and a structure containing an organic layer between them. In order to improve the efficiency and life of the organic electroluminescent element, the organic layer has a multilayer structure, and each layer contains different organic substances. Specifically, it can include a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, etc. In this organic electroluminescent element, when a voltage is applied between the two electrodes, holes are injected into the organic layer from the anode, and electrons are injected into the organic layer from the cathode. When the injected holes meet the electrons, excitons are formed, and light is emitted when the excitons transition back to the ground state. This organic electroluminescent element has the characteristics of self-luminescence, high brightness, high efficiency, low driving voltage, wide viewing angle, high contrast, and high responsiveness.

[0004] In order to improve the luminous performance of organic light-emitting diodes and promote the large-scale industrialization of organic light-emitting diodes, various organic optoelectronic material systems have been widely developed. However, although the existing materials have advantages in terms of luminous efficiency, they cannot achieve a satisfactory lifespan. Summary of the invention

[0005] In view of the above-mentioned deficiencies in the prior art, the object of the present invention is to provide an organic compound, a polymer, a mixture and a composition containing the same, and related organic electronic components, aiming to solve the problem of low performance, especially low lifespan, of existing organic electronic devices.

[0006] The technical solution of the present invention is as follows:

[0007] An organic compound having a structure as shown in general formula (I):

[0008]

[0009] in:

[0010] Ring A is selected from a substituted or unsubstituted aromatic or heteroaromatic group having 5 to 60 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups;

[0011] X are independently represented by N or CR1, and at least one X is N;

[0012] V1 is represented by CR2 or N;

[0013] V2 is represented by CR3 or N;

[0014] R1, R2, R3, at each occurrence, may be selected, identically or differently, from H, D, or a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 20 C atoms, or a branched or cyclic alkyl, alkoxy, thioalkoxy or silyl group having 3 to 20 C atoms, or a substituted keto group having 1 to 20 C atoms, or an alkoxycarbonyl group having 2 to 20 C atoms, or an aryloxycarbonyl group having 7 to 20 C atoms, or a cyano group, a carbamoyl group, or a cyclopentyl group. The invention further comprises a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, a haloformyl group, a formyl group, an isocyanate group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a nitro group, a CF3 group, a Cl group, a Br group, a F group, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these groups, wherein one or more of the groups can form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and / or with the ring to which the groups are bonded.

[0015] The present invention also relates to a polymer comprising at least one repeating unit, wherein the repeating unit comprises a structure corresponding to the organic compound as described above.

[0016] The present invention further relates to a mixture comprising a first organic compound (H1) and a second organic compound (H2), wherein the first organic compound (H1) comprises at least one organic compound as described above, the second organic compound (H2) has hole transport properties, and the molar ratio of the first organic compound (H1) to the second organic compound (H2) ranges from 1:9 to 9:1.

[0017] The present invention further relates to a composition comprising an organic compound or polymer or mixture as described above, and at least one organic solvent.

[0018] The present invention further relates to an organic electronic device comprising at least one organic compound or polymer or mixture as described above.

[0019] Beneficial effect: According to the organic compound of the present invention, triphenylsilicon group is used as a modifying group to modify triazine carbazole. The triphenylsilicon group can not only increase the steric hindrance of the compound, reduce the quenching effect caused by accumulation in the device, and improve the device efficiency, but also can utilize the hyperconjugation effect of Si atoms to reduce the triplet energy level of the host compound to a suitable position, which is more matched with the triplet energy level of the guest. However, if triphenylsilicon is directly connected to carbazole, the bond energy of carbazole connected to triazine will be reduced, which will reduce the device life. Therefore, it is very necessary to introduce a conjugated group on carbazole to reduce the influence of triphenylsilicon on the bond energy. Therefore, after first introducing a conjugated group on carbazole, it is better to introduce tetraphenylsilicon than directly connecting triphenylsilicon to triazine, and the main reason is that the influence of triphenylsilicon can be minimized to improve the device efficiency. In addition, the performance of the above-mentioned compound is further adjusted by adjusting different conjugated groups, so that the above-mentioned organic compound can be used not only as a blue light host material, but also as an electron transmission material or a green light material. DETAILED DESCRIPTION

[0020] The present invention provides an organic compound, a polymer, a mixture containing the same, a composition, and an application thereof in an organic electronic device. In order to make the purpose, technical scheme and effect of the present invention clearer and more specific, the present invention is further described in detail below. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0021] In the present invention, composition and printing ink, or ink have the same meaning and can be interchanged.

[0022] In the present invention, main material, matrix material, host or matrix material have the same meaning and can be interchanged.

[0023] In the present invention, metal organic complex, metal organic complex and organometallic complex have the same meaning and can be interchanged.

[0024] The present invention provides an organic compound having a structure as shown in the general formula (I):

[0025]

[0026] Wherein: Ring A is selected from a substituted or unsubstituted aromatic group or heteroaromatic group having 5 to 60 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups;

[0027] X is independently represented by N or CR1, and at least one X is N; V1 is represented by CR2 or N; V2 is represented by CR3 or N, and when V2 has a substituent, V2 is only represented by C;

[0028] R1, R2, R3, at each occurrence, may be selected, identically or differently, from H, D, or a straight-chain alkyl, alkoxy or thioalkoxy radical having 1 to 20 C atoms, or a branched or cyclic alkyl, alkoxy, thioalkoxy or silyl radical having 3 to 20 C atoms, or a substituted keto radical having 1 to 20 C atoms, or an alkoxycarbonyl radical having 2 to 20 C atoms, or an aryloxycarbonyl radical having 7 to 20 C atoms, or a cyano, carbamoyl, haloformyl radical A group comprising at least one aryl group, a hydroxyl group, a nitro group, a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, an aryloxy group or a heteroaryloxy group having 5 to 40 ring atoms, or a combination of these groups, wherein one or more of the groups can form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and / or with the ring to which the groups are bonded.

[0029] Aromatic ring system or aromatic group refers to a hydrocarbon group containing at least one aromatic ring, including monocyclic groups and polycyclic ring systems. Aromatic heterocyclic ring system or heteroaromatic group refers to a hydrocarbon group (containing heteroatoms) containing at least one aromatic heterocycle, including monocyclic groups and polycyclic ring systems. The heteroatoms are preferably selected from Si, N, P, O, S and / or Ge, and are particularly preferably selected from Si, N, P, O and / or S. These polycyclic rings can have two or more rings, in which two carbon atoms are shared by two adjacent rings, i.e., fused rings. At least one of these polycyclic ring species is aromatic or heteroaromatic. For the purpose of the present invention, aromatic or heteroaromatic ring systems include not only systems of aromatic or heteroaromatic groups, but also, wherein multiple aromatic or heteroaromatic groups can also be interrupted by short non-aromatic units (<10% of non-H atoms, preferably less than 5% of non-H atoms, such as C, N or O atoms). Thus, systems such as 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamines, diaryl ethers, etc. are also considered to be aromatic ring systems for the purposes of this invention.

[0030] Specific examples of the aromatic group include benzene, naphthalene, anthracene, phenanthrene, perylene, tetracene, pyrene, benzopyrene, triphenylene, acenaphthene, fluorene, and derivatives thereof.

[0031] Specific examples of heteroaromatic groups include furan, benzofuran, thiophene, benzothiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, indole, carbazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furanopyrrole, furanofuran, thienofuran, benzisoxazole, benzisothiazole, benzimidazole, pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, o-naphthylidene, quinoxaline, phenanthridine, primary idine, quinazoline, quinazolinone, and derivatives thereof.

[0032] In some embodiments, in the above organic compounds, ring A is an aryl ring or a heteroaryl ring, and at least one hydrogen in these rings may be substituted.

[0033] In some embodiments, Ring A, at each occurrence, is selected from a substituted or unsubstituted aromatic or heteroaromatic group having 6 to 50 ring atoms, or an aryloxy or heteroaryloxy group having 6 to 50 ring atoms, or a combination of these groups. In a preferred embodiment, Ring A, at each occurrence, is selected from a substituted or unsubstituted aromatic or heteroaromatic group having 6 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 6 to 40 ring atoms, or a combination of these groups. In some more preferred embodiments, Ring A, at each occurrence, is selected from a substituted or unsubstituted aromatic or heteroaromatic group having 6 to 30 ring atoms, or an aryloxy or heteroaryloxy group having 6 to 30 ring atoms, or a combination of these groups. In some more preferred embodiments, Ring A, at each occurrence, is selected from a substituted or unsubstituted aromatic or heteroaromatic group having 6 to 20 ring atoms, or an aryloxy or heteroaryloxy group having 6 to 20 ring atoms, or a combination of these groups. In some most preferred embodiments, each occurrence of Ring A is selected from a substituted or unsubstituted aromatic or heteroaromatic group having 6 to 15 ring atoms, or an aryloxy or heteroaryloxy group having 6 to 15 ring atoms, or a combination of these groups.

[0034] In some embodiments, in the above organic compound, ring A, at each occurrence, is independently selected from one or more combinations of the following structures:

[0035]

[0036] Each time V appears, it is independently selected from CR 101 or NR 102 ; W each time occurs, is independently selected from BR 103 、C(=O)、NR 104 , O, S, P, P=O or P=S; R 101 -R 104is selected, on each occurrence, identically or differently, from H, D, or a straight-chain alkyl, alkoxy or thioalkoxy radical having 1 to 20 C atoms, or a branched or cyclic alkyl, alkoxy, thioalkoxy or silyl radical having 3 to 20 C atoms, or a substituted keto radical having 1 to 20 C atoms, or an alkoxycarbonyl radical having 2 to 20 C atoms, or an aryloxycarbonyl radical having 7 to 20 C atoms, or a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a nitro group, CF3, Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic radical having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy radical having 5 to 40 ring atoms, or a combination of these groups; wherein one or more of the radicals can form a ring system with each other and / or with the radical to which they are bonded.

[0037] In certain embodiments, Ring A is selected from an aromatic ring system, a heteroaromatic ring system, or a fused-ring aromatic group.

[0038] In a preferred embodiment, the aromatic or heteroaromatic ring system is selected from the following groups:

[0039]

[0040] Wherein, the definitions of W and V are the same as above.

[0041] More preferably, the aromatic or heteroaromatic ring system is selected from the following groups:

[0042]

[0043] Wherein, the definitions of W and V are the same as above.

[0044] In a preferred embodiment, the condensed ring aromatic group is selected from: benzene, naphthalene, anthracene, fluoranthene, phenanthrene, triphenylene, dinaphthylene, tetracene, pyrene, benzopyrene, acenaphthene, fluorene, and derivatives thereof; the condensed ring heteroaromatic group is selected from: benzofuran, benzothiophene, indole, carbazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furanopyrrole, furanofuran, thienofuran, benzisoxazole, benzisothiazole, benzimidazole, quinoline, isoquinoline, o-naphthylidene, quinoxaline, phenanthridine, primary idine, quinazoline, quinazolinone, and derivatives thereof.

[0045] In certain embodiments, R1-R3, at each occurrence, may be independently selected from the following groups:

[0046]

[0047] Wherein: the definition of Y is the same as that of W above; the definition of Z is the same as that of V above; n1, n2, n3, n4 are all integers greater than or equal to 1.

[0048] In certain preferred embodiments, R1-R3, at each occurrence, may be independently selected from the following groups:

[0049]

[0050]

[0051] Among them: The H atoms on the ring can be further substituted.

[0052] In certain preferred embodiments, in the above organic compound, R1-R3 can be further selected from the following structural units or their combinations:

[0053]

[0054] Where n5 is 1 or 2 or 3 or 4.

[0055] In a more preferred embodiment, the above organic compound is at least partially deuterated, preferably 10% or more of the H is deuterated, more preferably 20% or more of the H is deuterated, very preferably 30% or more of the H is deuterated, and most preferably 40% or more of the H is deuterated.

[0056] In some preferred embodiments, the organic compound has a structure as shown in one of the general formulas (II-1) to (II-12):

[0057]

[0058]

[0059] Wherein: V1, V2, and X are defined as above.

[0060] In some more preferred embodiments, V1 cannot form a loop.

[0061] In some more preferred embodiments, the organic compound according to the present invention is selected from the general formula (V-1)-(V-3), (V-6)-(V-9).

[0062] In some more preferred embodiments, the organic compound according to the present invention is selected from the structure represented by one of the general formulas (III-1) to (III-12):

[0063]

[0064] Wherein: V1, V2, and X are defined as above.

[0065] In the embodiment of the present invention, the energy level structure of the organic material, the singlet energy level E S1 , triplet energy level ET1 , HOMO, and LUMO play a key role. The following is an introduction to the determination of these energy levels.

[0066] HOMO and LUMO energy levels can be measured by photoelectric effects, such as XPS (X-ray photoelectron spectroscopy) and UPS (ultraviolet photoelectron spectroscopy) or by cyclic voltammetry (hereafter referred to as CV). Recently, quantum chemical methods, such as density functional theory (hereafter referred to as DFT), have also become effective methods for calculating molecular orbital energy levels.

[0067] Singlet energy level E of organic materials S1 The triplet energy level E can be determined by the luminescence spectrum. T1 It can be measured by low temperature time-resolved luminescence spectroscopy, E S1 and E T1 It can also be obtained by quantum simulation calculation (such as by Time-dependent DFT), such as by commercial software Gaussian 09W (Gaussian Inc.), and the specific simulation method can be found in WO2011141110 or described in the examples below. ST Defined as (E S1 -E T1 ).

[0068] It should be noted that HOMO, LUMO, E S1 、E T1 The absolute value of depends on the measurement method or calculation method used. Even for the same method, different evaluation methods, such as the starting point and peak point on the CV curve, can give different HOMO / LUMO values. Therefore, reasonable and meaningful comparisons should be made using the same measurement method and the same evaluation method. In the description of the embodiments of the present invention, HOMO, LUMO, E S1 、E T1 The value is based on the Time-dependent DFT simulation and does not affect the application of other measurement or calculation methods.

[0069] In the present invention, (HOMO-1) is defined as the second highest occupied orbital energy level, (HOMO-2) is the third highest occupied orbital energy level, and so on. (LUMO+1) is defined as the second lowest unoccupied orbital energy level, (LUMO+2) is the third lowest occupied orbital energy level, and so on.

[0070] The organic compound according to the present invention can be used as an organic functional material in an electronic device. The organic functional material can be divided into a hole injection material (HIM), a hole transport material (HTM), an electron transport material (ETM), an electron injection material (EIM), an electron blocking material (EBM), a hole blocking material (HBM), an emitter, and a host material (Host). In a preferred embodiment, the organic compound according to the present invention can be used as a host material, an electron transport material, or a hole blocking material. In a more preferred embodiment, the organic compound according to the present invention can be used as a phosphorescent host material.

[0071] As a phosphorescent host material, it must have an appropriate triplet energy level, namely, E T1 In certain embodiments, the organic compound according to the present invention has E T1 ≥2.4eV, preferably ≥2.5eV, more preferably ≥2.6eV, most preferably ≥2.7eV.

[0072] In certain preferred embodiments, the organic compounds according to the present invention have a small singlet-triplet energy level difference, typically ΔE st ≤0.3eV, preferably ΔE st ≤0.2eV, preferably ΔE st ≤0.15eV, preferably ΔE st ≤0.10eV.

[0073] As a phosphorescent host material, it is desirable to have good thermal stability. Generally, the organic compound according to the present invention has a glass transition temperature (Tg) ≥ 100°C; in a preferred embodiment, Tg ≥ 120°C; in a more preferred embodiment, Tg ≥ 140°C; in a more preferred embodiment, Tg ≥ 160°C; in a most preferred embodiment, Tg ≥ 180°C.

[0074] In certain preferred embodiments, the organic compound according to the present invention has (HOMO-(HOMO-1)) ≥ 0.2 eV, preferably ≥ 0.25 eV, more preferably ≥ 0.3 eV, even better ≥ 0.35 eV, very preferably ≥ 0.4 eV, and most preferably ≥ 0.45 eV.

[0075] In some more preferred embodiments, the organic compound according to the present invention has ((LUMO+1)-LUMO)≥0.2eV, preferably ≥0.25eV, better ≥0.3eV, even better ≥0.35eV, very best ≥0.4eV, and most preferably ≥0.45eV.

[0076] In a more preferred embodiment, the organic compound according to the present invention is partially deuterated, preferably 10% or more of the H is deuterated, more preferably 20% or more of the H is deuterated, very preferably 30% or more of the H is deuterated, and most preferably 40% or more of the H is deuterated.

[0077] In a preferred embodiment, the organic compound of the present invention is used in an evaporation-type OLED device. For this purpose, the organic compound according to the present invention has a molecular weight of ≤1000 g / mol, preferably ≤900 g / mol, very preferably ≤850 g / mol, more preferably ≤800 g / mol, and most preferably ≤700 g / mol.

[0078] Specific examples of the organic compound represented by the general formula (I) according to the present invention are listed below, but the present invention is not limited thereto.

[0079]

[0080]

[0081]

[0082]

[0083]

[0084] The present invention also relates to a polymer comprising at least one repeating unit, wherein the repeating unit comprises at least one structure corresponding to the above organic compound. In certain embodiments, the polymer is a non-conjugated polymer, wherein the structural unit corresponding to the above organic compound is on the side chain. In another preferred embodiment, the polymer is a conjugated polymer.

[0085] The term "small molecule" as defined herein refers to a molecule that is not a polymer, oligomer, dendrimer, or blend. In particular, there is no repeating structure in a small molecule. The molecular weight of a small molecule is ≤3000 g / mol, preferably ≤2000 g / mol, and most preferably ≤1500 g / mol.

[0086] Polymers include homopolymers, copolymers, and block copolymers. In the present invention, polymers also include dendrimers. For the synthesis and application of dendrimers, please refer to [Dendrimers and Dendrons, Wiley-VCH Verlag GmbH & Co. KGaA, 2002, Ed. George R. Newkome, Charles N. Moorefield, Fritz Vogtle.].

[0087] In a preferred embodiment, the synthesis method of the polymer is selected from SUZUKI-, YAMAMOTO-, STILLE-, NIGESHI-, KUMADA-, HECK-, SONOGASHIRA-, HIYAMA-, FUKUYAMA-, HARTWIG-BUCHWALD- and ULLMAN.

[0088] In a preferred embodiment, the polymer according to the present invention has a glass transition temperature (Tg) ≥ 100°C, preferably ≥ 120°C, more preferably ≥ 140°C, more preferably ≥ 160°C, and most preferably ≥ 180°C.

[0089] In a preferred embodiment, the molecular weight distribution (PDI) of the polymer according to the present invention is preferably in the range of 1-5; more preferably 1-4; more preferably 1-3; even more preferably 1-2; and most preferably 1-1.5.

[0090] In a preferred embodiment, the weight average molecular weight (Mw) of the polymer according to the present invention is preferably in the range of 10,000-1,000,000; more preferably 50,000-500,000; more preferably 100,000-400,000; even more preferably 150,000-300,000; and most preferably 200,000-250,000.

[0091] The present invention also relates to a mixture, comprising an organic compound as described above or a polymer as described above, and at least another organic functional material, wherein the another organic functional material is selected from a hole injection material (HIM), a hole transport material (HTM), an electron transport material (ETM), an electron injection material (EIM), an electron blocking material (EBM), a hole blocking material (HBM), an emitter, a host material (Host) or an organic dye. For example, various organic functional materials are described in detail in WO2010135519A1, US20090134784A1 and WO2011110277A1, and the entire contents of these three patent documents are hereby incorporated herein by reference. The organic functional material can be a small molecule and a polymer material.

[0092] In a preferred embodiment, the mixture comprises an organic compound or polymer according to the present invention and a phosphorescent emitter. Here, the organic compound according to the present invention can be used as the main body, and the weight percentage of the phosphorescent emitter is ≤20wt%, preferably ≤15wt%, and more preferably ≤10wt%.

[0093] In another preferred embodiment, the mixture comprises an organic compound or polymer according to the present invention, another host material and a phosphorescent emitter. Here, the organic compound according to the present invention is used as a co-host material, and its weight percentage is ≥10wt%, preferably ≥20wt%, more preferably ≥30wt%, and most preferably ≥40wt%.

[0094] In a more preferred embodiment, the mixture comprises an organic compound or polymer according to the present invention, a phosphorescent light emitter and a host material. In this embodiment, the organic compound according to the present invention can be used as an auxiliary light emitting material, and the weight ratio of the organic compound according to the present invention to the phosphorescent light emitter is from 1:2 to 2:1. In another preferred embodiment, the organic compound according to the present invention has an E T1 Higher than the phosphorescent emitters.

[0095] In certain embodiments, the mixture comprises an organic compound or polymer according to the present invention, and another TADF material.

[0096] In some more preferred embodiments, the mixture according to the present invention includes an organic functional material selected from the organic compounds or polymers described above, and at least another organic functional material selected from hole (also known as hole) injection or transport material (HIM / HTM) and organic host material (Host).

[0097] The present invention also relates to a mixture comprising a first organic compound (H1) and a second organic compound (H2), wherein the first organic compound (H1) comprises at least one organic compound as described above, the second organic compound (H2) has hole transport properties, and the molar ratio of the first organic compound (H1) to the second organic compound (H2) ranges from 1:9 to 9:1.

[0098] In a preferred embodiment, the first organic compound (H1) and the second organic compound (H2) have a type II semiconductor heterojunction structure, wherein the first organic compound (H1) comprises a structural unit represented by the general formula (I), and min((LUMO(H1)-HOMO(H2), LUMO(H2)-HOMO(H1))≤min(ET(H1), ET(H2))+0.1eV, wherein LUMO(H1), HOMO(H1) and ET(H1) correspond to the lowest unoccupied orbital, highest occupied orbital and triplet energy level of the first organic compound (H1), respectively, and LUMO(H2), HOMO(H2) and ET(H2) correspond to the lowest unoccupied orbital, highest occupied orbital and triplet energy level of the second organic compound (H2), respectively.

[0099] In certain preferred embodiments, according to the mixture of the present invention, at least one of the first compound (H1) and the second compound (H2) has ((LUMO+1)-LUMO) ≥ 0.2eV, preferably ≥ 0.25eV, better ≥ 0.3eV, even better ≥ 0.35eV, very best ≥ 0.4eV, and most preferably ≥ 0.45eV.

[0100] In a more preferred embodiment, according to the mixture of the present invention, the ((LUMO+1)-LUMO) of the first compound (H1) is ≥0.2eV, preferably ≥0.25eV, better ≥0.3eV, even better ≥0.35eV, very best ≥0.4eV, and most preferably ≥0.45eV.

[0101] In certain preferred embodiments, according to the mixture of the present invention, at least one of the first compound (H1) and the second compound (H2) has (HOMO-(HOMO-1)) ≥ 0.2eV, preferably ≥ 0.25eV, better ≥ 0.3eV, even better ≥ 0.35eV, very best ≥ 0.4eV, and most preferably ≥ 0.45eV.

[0102] In a more preferred embodiment, according to the mixture of the present invention, the (HOMO-(HOMO-1)) of the second compound (H2) is ≥0.2eV, preferably ≥0.25eV, better ≥0.3eV, even better ≥0.35eV, very best ≥0.4eV, and most preferably ≥0.45eV.

[0103] In certain more preferred embodiments, the mixture, wherein 1) the ΔE(S1-T1) of the first compound (H1) is ≤0.30eV, preferably ≤0.25eV, more preferably ≤0.20eV, most preferably ≤0.10eV, and / or 2) the LUMO of the second compound (H2) is higher than the LUMO of the first compound (H1), and the HOMO of the second compound (H2) is lower than the HOMO of the first compound (H1).

[0104] In certain preferred embodiments, the mixture, wherein the first compound (H1) and the second compound (H2) have a type II semiconductor heterojunction structure, and min((LUMO(H1)-HOMO(H2), LUMO(H2)-HOMO(H1))≤min(ET(H1), ET(H2))+0.1 eV, wherein LUMO(H1), HOMO(H1) and ET(H1) are the lowest unoccupied orbital, the highest occupied orbital, and the triplet energy level of H1, respectively, and LUMO(H2) is 2), HOMO(H2) and ET(H2) are the lowest unoccupied orbital, highest occupied orbital and triplet energy levels of H2, respectively. It is more preferred that min((LUMO(H1)-HOMO(H2),LUMO(H2)-HOMO(H1))≤min(ET(H1),ET(H2)); more preferably, min((LUMO(H1)-HOMO(H2),LUMO(H2)-HOMO(H1))≤min(ET(H1),ET(H2))-0.1 eV.

[0105] In a preferred embodiment, the first compound (H1) and the second compound (H2) have a semiconductor heterojunction structure of type I, and the singlet energy level and triplet energy level difference ΔE of the first compound (H1) or the second compound (H2) is ST ≤0.25 eV, preferably ≤0.20 eV, more preferably ≤0.15 eV, most preferably ≤0.10 eV.

[0106] In a preferred embodiment, the mixture, wherein the molar ratio of the first compound (H1) to the second compound (H2) is from 1:9 to 9:1; the preferred molar ratio is 2:8 to 8:2; the more preferred molar ratio is 3:7 to 7:3; the more preferred molar ratio is 4:6 to 6:4; the most preferred molar ratio is 4.5:5.5 to 5.5:4.5.

[0107] In a preferred embodiment, the mixture, wherein the difference in molecular weight between the first compound (H1) and the second compound (H2) is not more than 100 Dalton, preferably not more than 80 Dalton, more preferably not more than 70 Dalton, even better not more than 60 Dalton, very preferably not more than 40 Dalton, and most preferably not more than 30 Dalton.

[0108] In another preferred embodiment, the mixture, wherein the difference in sublimation temperature between the first compound (H1) and the second compound (H2) is no more than 50K; more preferably, the difference in sublimation temperature is no more than 30K; even more preferably, the difference in sublimation temperature is no more than 20K; and most preferably, the difference in sublimation temperature is no more than 10K.

[0109] In a preferred embodiment, according to the mixture of the present invention, at least one of the first compound (H1) and the second compound (H2) has a glass transition temperature (Tg) ≥ 100°C; in a more preferred embodiment, at least one has a Tg ≥ 120°C; in a more preferred embodiment, at least one has a Tg ≥ 140°C; in an even more preferred embodiment, at least one has a Tg ≥ 160°C; in a most preferred embodiment, at least one has a Tg ≥ 180°C.

[0110] In some embodiments, the second organic compound (H2) in the mixture is selected from the general formula (V-1), or a combination of the general formula (V-2) and the general formula (V-3), or any one of the general formula (V-4):

[0111]

[0112] Wherein: G1, G2 are each independently selected from substituted or unsubstituted aromatic or heteroaromatic groups having 6 to 30 ring atoms; K is each independently a single bond or CR 12 R 13 ; s is 0 or 1 independently at each occurrence; two adjacent * in general formula (V-2) are connected to two * in general formula (V-3), and the * in general formula (V-2) not connected to general formula (V-3) is CR 14; L1-L3 are independently selected from substituted or unsubstituted aromatic groups or heteroaromatic groups having 6 to 30 ring atoms; R4-R 14 The definition is the same as that of R1; Ar1-Ar3 are independently selected from substituted or unsubstituted aromatic groups having 6 to 30 ring atoms or heteroaromatic groups having 2 to 30 ring atoms; n1 is selected from an integer from 0 to 7; n2 is selected from an integer from 0 to 8.

[0113] In some more preferred embodiments, the second organic compound (H2) in the mixture is a compound represented by one of the following general formulas (VI-1) to (VI-10):

[0114]

[0115] Among them, G1, G2, s, K, R4-R 11 , L1-L3, Ar1-Ar3, n1, n2 are as defined above, R 15 The definition is the same as that of R1 above.

[0116] Specific examples of the second organic compound (H2) are shown below, but are not limited thereto:

[0117]

[0118]

[0119]

[0120] The main material, phosphorescent material and TADF material are described in some detail below (but not limited to this).

[0121] 1. Triplet Host

[0122] Examples of triplet host materials are not particularly limited. Any metal complex or organic compound may be used as a host, as long as its triplet energy level is higher than that of a light emitter, particularly a triplet light emitter or a phosphorescent light emitter. Examples of metal complexes that can be used as triplet hosts include (but are not limited to) the following general structures:

[0123]

[0124] Wherein: M3 is a metal; (Y1-Y2) is a bidentate ligand, Y3 and Y4 are independently selected from C, N, O, P or S; L is an auxiliary ligand; r2 is an integer ranging from 1 to the maximum coordination number of the metal; In a preferred embodiment, the metal complex that can be used as a triplet host has the following form:

[0125]

[0126] Where: (ON) is a didentate ligand in which the metal is coordinated to O and N atoms, r2 is an integer ranging from 1 to the maximum coordination number of the metal;

[0127] In one embodiment, M3 can be selected from Ir and Pt.

[0128] Examples of organic compounds that can serve as triplet hosts are selected from compounds containing cyclic aromatic hydrocarbon groups, such as benzene, biphenyl, triphenylbenzene, benzofluorene; compounds containing aromatic heterocyclic groups, such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, dibenzocarbazole, indolecarbazole, pyridineindole, pyrroledipyridine, pyrazole, imidazole, triazoles, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazines, oxazines, oxathiazines, oxadiazines, indoles, benzimidazoles, indazoles, oxazoles, diphenyl oxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, o-naphthyridine, quinazoline, quinoxaline, naphthalene, phthalein, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuran pyridine, furopyridine, benzothiophene pyridine, thiophene pyridine, benzoselenophene pyridine and selenophene benzodipyridine; groups containing 2 to 10 ring structures, which can be the same or different types of cyclic aromatic hydrocarbon groups or aromatic heterocyclic groups, and are directly or through at least one of the following groups linked together, such as oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, phosphorus atoms, boron atoms, chain structure units and aliphatic ring groups. Wherein, each Ar can be further substituted, and the substituent can be selected from hydrogen, deuterium, cyano, halogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl.

[0129] In a preferred embodiment, the triplet host material may be selected from compounds comprising at least one of the following groups:

[0130]

[0131] Wherein: Ar4-Ar6 have the same meaning as Ar1 described above; X 1 –X 9 Independently selected from CR 1 R 2 or NR 1 ; Y3 is selected from CR 8 R 9 , NR 8 , O or S; R 1 -R 9 The meaning is the same as R1 above, n6 is the same or different at each occurrence and is independently selected from any integer from 0 to 5.

[0132] Examples of suitable triplet host materials are listed below but are not limited to:

[0133]

[0134] 2. Triplet Emitter

[0135] Triplet emitters are also called phosphorescent emitters. In a preferred embodiment, the triplet emitter is a metal complex having the general formula M(L)n, wherein M is a metal atom, L can be the same or different each time it appears, is an organic ligand, which is bonded or coordinated to the metal atom M through one or more positions, and n is an integer greater than 1, preferably 1, 2, 3, 4, 5 or 6. Optionally, these metal complexes are linked to a polymer through one or more positions, preferably through an organic ligand.

[0136] In a preferred embodiment, the metal atom M is selected from transition metal elements, lanthanides or actinides, preferably Ir, Pt, Pd, Au, Rh, Ru, Os, Sm, Eu, Gd, Tb, Dy, Re, Cu or Ag, and particularly preferably Os, Ir, Ru, Rh, Re, Pd, Au or Pt.

[0137] Preferably, the triplet emitter contains a chelating ligand, i.e. a ligand that coordinates to the metal via at least two binding points, and it is particularly preferred that the triplet emitter contains two or three identical or different bidentate or multidentate ligands. Chelating ligands are beneficial for improving the stability of the metal complex.

[0138] Examples of organic ligands may be selected from phenylpyridine derivatives, 7,8-benzoquinoline derivatives, 2(2-thienyl)pyridine derivatives, 2(1-naphthyl)pyridine derivatives, or 2-phenylquinoline derivatives. All of these organic ligands may be substituted, for example, by fluorine-containing or trifluoromethyl groups. The auxiliary ligand may be preferably selected from acetic acid, acetone or picric acid.

[0139] In a preferred embodiment, the metal complex useful as triplet emitter has the following form:

[0140]

[0141] Wherein M is a metal selected from transition metal elements or lanthanide or actinide elements, and particularly preferably Ir, Pt, Au.

[0142] Ar 1 Each occurrence may be the same or different and is a cyclic group containing at least one donor atom, i.e. an atom with a lone pair of electrons, such as nitrogen or phosphorus, through which the cyclic group is coordinated to the metal; Ar 2Each occurrence may be the same or different and is a cyclic group containing at least one C atom through which the cyclic group is attached to the metal; Ar 1 and Ar 2 They are linked together by covalent bonds and may each carry one or more substituent groups, and they may also be linked together by substituent groups; L' may be the same or different each time it appears, and is a bidentate chelating auxiliary ligand, preferably a monoanionic bidentate chelating ligand; q1 may be 0, 1, 2 or 3, preferably 2 or 3; q2 may be 0, 1, 2 or 3, preferably 1 or 0.

[0143] Examples of some triplet emitter materials and their applications can be found in the following patent documents and literature: WO200070655, WO200141512, WO200202714, WO200215645, EP1191613, EP1191612, EP1191614, WO2005033244, WO2005019373, US2005 / 0258742, WO200914 6770, WO2010015307, WO2010031485, WO2010054731, WO2010054728, WO2010086089, WO20100998 52. WO2010102709, US20070087219A1, US20090061681A1, US20010053462A1, Baldo, Thompsonnet al.Nature 403,(2000),750-753, Adachi et al.Appl.Phys.Lett.78(2001),1622-1624, J.Kido et al.Appl.Phys.Lett.65(1994),2124, Kido et al. al.Chem.Lett.657,1990, US2007 / 0252517A1, Johnson et al., JACS105,1983,1795, Wrighton, JACS 96,1974,998, Ma etal.,Synth.Metals 94,1998,245, US6824895, US7029766, US6835469, US6830828, US20010053462A1, WO2007095118A1, US20 12004407A1, WO2012007088A1, WO2012007087A1, WO2012007086A1, US2008027220A1, WO2011157339A1, CN The entire contents of the above-listed patent documents and literature are hereby incorporated by reference into this document.

[0144] Some examples of suitable triplet emitters are listed below:

[0145]

[0146]

[0147] 3. TADF materials

[0148] Traditional organic fluorescent materials can only utilize 25% of the singlet excitons formed by electrical excitation to emit light, and the internal quantum efficiency of the device is low (up to 25%). Although phosphorescent materials can effectively utilize singlet excitons and triplet excitons formed by electrical excitation to emit light due to the strong spin-orbit coupling of the heavy atom center, the internal quantum efficiency of the device can reach 100%. However, the expensive phosphorescent materials, poor material stability, and serious device efficiency roll-off limit their application in OLEDs. Thermally activated delayed fluorescence luminescent materials are the third generation of organic light-emitting materials developed after organic fluorescent materials and organic phosphorescent materials. This type of material generally has a small singlet-triplet energy level difference (ΔEst), and triplet excitons can be transformed into singlet excitons through anti-intersystem crossing. This can make full use of singlet excitons and triplet excitons formed under electrical excitation. The internal quantum efficiency of the device can reach 100%. At the same time, the material structure is controllable, the properties are stable, the price is cheap, and no precious metals are required, and the application prospects in the field of OLED are broad.

[0149] TADF materials need to have a small singlet-triplet energy level difference, preferably ΔEst < 0.3 eV, second best ΔEst < 0.2 eV, and most preferably ΔEst < 0.1 eV. In a preferred embodiment, the TADF material has a relatively small ΔEst. In another preferred embodiment, TADF has a good fluorescence quantum efficiency. Some TADF luminescent materials can be found in the following patent documents: CN103483332 (A), TW201309696 (A), TW201309778 (A), TW201343874 (A), TW201350558 (A), US20120217869 (A1), WO2013133359 (A1), WO2013154064 (A1), Adachi, et.al. Adv. Mater.,21,2009,4802,Adachi,et.al.Appl.Phys.Lett.,98,2011,083302,Adachi,et.al.Appl.Phys.Lett.,101,2012,093306,Adachi,et.al.Chem.Commun.,48,2012,11392,Adachi,et.al.Nature Photonics, 6, 2012, 253, Adachi, et.al. Nature, 492, 2012, 234, Adachi, et.al. J. Am. Chem. Soc, 134, 2012, 14706, Adachi, et. al. Angew. Chem. Int.Ed,51,2012,11311,Adachi,et.al.Chem.Commun.,48,2012,9580,Adachi,et.al.Chem.Commun.,49,2013,10385,Adachi,et.al.Adv.Mate r., 25, 2013, 3319, Adachi, et.al. Adv. Mater., 25, 2013, 3707, Adachi, et.al. Chem. Mater., 25, 2013, 3038, Adachi, et.al. Chem. Mater., 25, 2013, 3766, Adachi, et.al. J. Mater. Chem. C., 1, 2013, 4599, Adachi, et.al. J. Phys. Chem. A., 117, 2013, 5607, the entire contents of the above-listed patents or article documents are hereby incorporated herein by reference.

[0150] Some examples of suitable TADF emitters are listed below:

[0151]

[0152]

[0153] In a preferred embodiment, the organic compound according to the invention is used in a vapor deposition type OLED device. For this purpose, the organic compound according to the invention has a molecular weight of ≤1000 g / mol, preferably ≤900 g / mol, very preferably ≤850 g / mol, more preferably ≤800 g / mol, and most preferably ≤700 g / mol.

[0154] Another object of the present invention is to provide a material solution for printed OLEDs.

[0155] For this purpose, organic compounds according to the invention have a molecular weight of ≥700 g / mol, preferably ≥800 g / mol, very preferably ≥900 g / mol, more preferably ≥1000 g / mol and most preferably ≥1100 g / mol.

[0156] In other preferred embodiments, the solubility of the organic compound according to the present invention in toluene at 25° C. is ≥10 mg / mL, preferably ≥15 mg / mL, and most preferably ≥20 mg / mL.

[0157] The present invention further relates to a composition or ink comprising an organic compound or polymer or mixture according to the present invention and at least one organic solvent.

[0158] When used in printing processes, the viscosity and surface tension of the ink are important parameters. The appropriate surface tension parameters of the ink are suitable for a specific substrate and a specific printing method.

[0159] In a preferred embodiment, the surface tension of the ink according to the present invention at operating temperature or at 25°C is approximately in the range of 19 dyne / cm to 50 dyne / cm; more preferably in the range of 22 dyne / cm to 35 dyne / cm; and most preferably in the range of 25 dyne / cm to 33 dyne / cm.

[0160] In another preferred embodiment, the viscosity of the ink according to the present invention at the working temperature or 25° C. is about 1 cps-100 cps; preferably 1 cps-50 cps; more preferably 1.5 cps-20 cps; most preferably 4 cps-20 cps. The composition thus formulated will facilitate inkjet printing.

[0161] The viscosity can be adjusted by different methods, such as by selecting a suitable solvent and the concentration of the functional material in the ink. The ink containing the organic compound or polymer or mixture according to the present invention can facilitate people to adjust the printing ink in an appropriate range according to the printing method used. Generally, the weight ratio of the functional material contained in the composition according to the present invention is in the range of 0.3wt% to 30wt%, preferably in the range of 0.5wt% to 20wt%, more preferably in the range of 0.5wt% to 15wt%, more preferably in the range of 0.5wt% to 10wt%, and the best is in the range of 1wt% to 5wt%.

[0162] In some embodiments, according to the ink of the present invention, the at least one organic solvent is selected from aromatic or heteroaromatic based solvents, in particular aliphatic chain / ring substituted aromatic solvents, or aromatic ketone solvents, or aromatic ether solvents.

[0163] Examples of solvents suitable for the present invention include, but are not limited to: aromatic or heteroaromatic based solvents: p-diisopropylbenzene, pentylbenzene, tetralin, cyclohexylbenzene, chloronaphthalene, 1,4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, dipentylbenzene, tripentylbenzene, pentyltoluene, o-xylene, m-xylene, p-xylene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1,2,3,4-tetralin, 1,2,3,5-tetralin, 1,2,4,5-tetralin, butylbenzene, dodecylbenzene, dihexylbenzene, dibutylbenzene, p-diisopropylbenzene, 1-methoxynaphthalene, cyclohexylbenzene, dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, 1-methylnaphthalene, 1,2,4-trichloronaphthalene. Benzene, 1,3-dipropoxybenzene, 4,4-difluorodiphenylmethane, 1,2-dimethoxy-4-(1-propenyl)benzene, diphenylmethane, 2-phenylpyridine, 3-phenylpyridine, N-methyldiphenylamine, 4-isopropylbiphenyl, 4-(3-phenylpropyl)pyridine, benzyl benzoate, 1,1-bis(3,4-dimethylphenyl)ethane, 2-isopropylnaphthalene, dibenzyl ether, etc.; ketone-based solvents: 1-tetralone, 2-tetralone, 2-(phenylepoxy)tetralone, 6-(methoxy)tetralone, acetophenone, propiophenone, benzophenone, and their derivatives, such as 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4-methylpropiophenone , 3-methylpropiophenone, 2-methylpropiophenone, isophorone, 2,6,8-trimethyl-4-nonanone, fenchone, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 2,5-hexanedione, phorone, di-n-amyl ketone; aromatic ether solvents: 3-phenoxytoluene, butoxybenzene, benzylbutylbenzene, p-anisaldehyde dimethyl acetal, tetrahydro-2-phenoxy-2H-pyran, 1,2-dimethoxy-4-(1-propenyl)benzene, 1,4-benzodioxane, 1,3-dipropylbenzene, 2,5-dimethoxytoluene, 4-ethylphenyl ether, 1,2,4-trimethoxybenzene, 4-(1-propenyl)-1,2-dimethoxybenzene, 1,3-dimethoxy Benzene, glycidyl phenyl ether, dibenzyl ether, 4-tert-butylanisole, trans-p-propenylanisole, 1,2-dimethoxybenzene, 1-methoxynaphthalene, diphenyl ether, 2-phenoxymethyl ether, 2-phenoxytetrahydrofuran, ethyl-2-naphthyl ether, amyl ether, hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether; ester solvents: alkyl octanoate, alkyl sebacate, alkyl stearate, alkyl benzoate, alkyl phenylacetate, alkyl cinnamate, alkyl oxalate, alkyl maleate, alkyl lactone, alkyl oleate, etc.

[0164] Further, according to the ink of the present invention, the at least one organic solvent can be selected from: aliphatic ketones, for example, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 2,5-hexanedione, 2,6,8-trimethyl-4-nonanone, phorone, di-n-amyl ketone, etc.; or aliphatic ethers, for example, amyl ether, hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, etc.

[0165] In some other embodiments, the printing ink further comprises another organic solvent. Examples of the other organic solvent include (but are not limited to): methanol, ethanol, 2-methoxyethanol, dichloromethane, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, toluene, o-xylene, m-xylene, p-xylene, 1,4-dioxane, acetone, methyl ethyl ketone, 1,2-dichloroethane, 3-phenoxytoluene, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetralin, decalin, indene and / or mixtures thereof.

[0166] In a preferred embodiment, the composition according to the present invention is a solution.

[0167] In another preferred embodiment, the composition according to the present invention is a suspension.

[0168] The composition in the embodiment of the present invention may include 0.01wt% to 20wt% of the organic compound or polymer or mixture according to the present invention, preferably 0.1wt% to 15wt%, more preferably 0.2wt% to 10wt%, and most preferably 0.25wt% to 5wt% of the organic compound or polymer or mixture.

[0169] The present invention also relates to the use of the composition as a coating or printing ink in the preparation of organic electronic devices, and particularly preferably a preparation method by printing or coating.

[0170] Among them, suitable printing or coating techniques include (but are not limited to) inkjet printing, nozzle printing, gravure printing, letterpress printing, screen printing, dip coating, spin coating, doctor blade coating, roller printing, twist roller printing, lithography, flexographic printing, rotary printing, spraying, brushing or pad printing, slot extrusion coating, etc. The preferred ones are inkjet printing, nozzle printing and gravure printing. The solution or suspension may further include one or more components such as surfactant compounds, lubricants, wetting agents, dispersants, hydrophobic agents, adhesives, etc., for adjusting viscosity, film-forming properties, improving adhesion, etc. For detailed information on printing technology and its related requirements for related solutions, such as solvents, concentrations, viscosities, etc., please refer to the "Handbook of Print Media: Technologies and Production Methods" edited by Helmut Kipphan, ISBN 3-540-67326-1.

[0171] Based on the above organic compound or polymer, the present invention also provides an application of the above organic compound or polymer, that is, the organic compound or polymer is applied to an organic electronic device, the organic electronic device can be selected from, but not limited to, an organic light emitting diode (OLED), an organic photovoltaic cell (OPV), an organic light emitting cell (OLEEC), an organic field effect transistor (OFET), an organic light emitting field effect transistor, an organic laser, an organic spin electronic device, a photodiode, an organic sensor and an organic plasmon emitting diode (Organic Plasmon Emitting Diode), etc., and organic electroluminescent devices such as OLED, OLEEC, and organic light emitting field effect transistor are particularly preferred. Preferably, the organic compound or polymer is used in the light emitting layer of the electroluminescent device.

[0172] The present invention further relates to an organic electronic device, comprising at least one organic compound or polymer or mixture as described above. Generally, such an organic electronic device comprises at least one cathode, an anode and a functional layer between the cathode and the anode, wherein the functional layer comprises at least one organic compound or polymer or mixture as described above. The organic electronic device can be selected from, but not limited to, organic light emitting diodes (OLEDs), organic photovoltaic cells (OPVs), organic light emitting cells (OLEECs), organic field effect transistors (OFETs), organic light emitting field effect transistors, organic lasers, organic spintronic devices, photodiodes, photodiodes, organic sensors and organic plasmon emitting diodes (Organic Plasmon Emitting Diodes), etc., and organic electroluminescent devices such as OLEDs, OLEECs and organic light emitting field effect transistors are particularly preferred.

[0173] In some particularly preferred embodiments, the organic electronic device is an organic electroluminescent device, which comprises a substrate, an anode, at least one light-emitting layer, a cathode, and optionally a hole transport layer. In some embodiments, the hole transport layer comprises an organic compound or polymer or mixture according to the present invention. In a preferred embodiment, the light-emitting layer comprises an organic compound or polymer or mixture according to the present invention. More preferably, the light-emitting layer comprises an organic compound or polymer or mixture according to the present invention, and at least one light-emitting material, and the light-emitting material can be preferably selected from fluorescent light emitters, phosphorescent light emitters or TADF materials.

[0174] In certain particularly preferred embodiments, the organic electronic device is an organic electroluminescent device and comprises an electron transport layer or a hole blocking layer comprising at least one organic compound according to the present invention.

[0175] The device structure of the organic electroluminescent device is described below, but is not limited to this.

[0176] The substrate can be opaque or transparent. A transparent substrate can be used to make a transparent light-emitting device. For example, see Bulovic et al. Nature 1996, 380, p29, and Gu et al., Appl. Phys. Lett. 1996, 68, p2606. The substrate can be rigid or elastic. The substrate can be plastic, metal, semiconductor wafer or glass. It is best that the substrate has a smooth surface. Substrates without surface defects are particularly ideal. In a preferred embodiment, the substrate is flexible and can be selected from a polymer film or plastic, and its glass transition temperature (Tg) is above 150°C, preferably above 200°C, more preferably above 250°C, and preferably above 300°C. Examples of suitable flexible substrates are polyethylene terephthalate (PET) and polyethylene glycol (2,6-naphthalene) (PEN).

[0177] The anode may comprise a conductive metal or metal oxide, or a conductive polymer. The anode can easily inject holes into the hole injection layer (HIL) or the hole transport layer (HTL) or the light-emitting layer. In a preferred embodiment, the absolute value of the difference between the work function of the anode and the HOMO level or valence band level of the light emitter in the light-emitting layer or the p-type semiconductor material as the HIL or HTL or the electron blocking layer (EBL) is less than 0.5 eV, preferably less than 0.3 eV, and most preferably less than 0.2 eV. Examples of anode materials include but are not limited to: Al, Cu, Au, Ag, Mg, Fe, Co, Ni, Mn, Pd, Pt, ITO, aluminum-doped zinc oxide (AZO), etc. Other suitable anode materials are known and can be easily selected for use by a person skilled in the art. The anode material can be deposited using any suitable technique, such as a suitable physical vapor deposition method, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), etc. In some embodiments, the anode is patterned. Patterned ITO conductive substrates are commercially available and can be used to prepare devices according to the present invention.

[0178] The cathode may comprise a conductive metal or metal oxide. The cathode can easily inject electrons into the EIL or ETL or directly into the light-emitting layer. In a preferred embodiment, the absolute value of the difference between the work function of the cathode and the LUMO energy level or conduction band energy level of the luminophore in the light-emitting layer or the n-type semiconductor material as the electron injection layer (EIL) or the electron transport layer (ETL) or the hole blocking layer (HBL) is less than 0.5 eV, preferably less than 0.3 eV, and most preferably less than 0.2 eV. In principle, all materials that can be used as cathodes of OLEDs may be used as cathode materials for the device of the present invention. Examples of cathode materials include but are not limited to: Al, Au, Ag, Ca, Ba, Mg, LiF / Al, MgAg alloy, BaF2 / Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO, etc. The cathode material can be deposited using any suitable technique, such as a suitable physical vapor deposition method, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), etc.

[0179] OLEDs may also include other functional layers, such as a hole injection layer (HIL), a hole transport layer (HTL), an electron blocking layer (EBL), an electron injection layer (EIL), an electron transport layer (ETL), and a hole blocking layer (HBL). Materials suitable for use in these functional layers are described in detail above.

[0180] In another preferred embodiment, in the light-emitting device according to the present invention, the electron transport layer (ETL) or the hole blocking layer (HBL) thereof comprises the organic compound or polymer according to the present invention and is prepared by a solution processing method.

[0181] According to the light emitting device of the present invention, the light emitting wavelength is between 300nm and 1000nm, preferably between 350nm and 900nm, and more preferably between 400nm and 800nm.

[0182] The present invention also relates to the application of the electroluminescent device according to the present invention in various electronic devices, including, but not limited to, display devices, lighting devices, light sources, sensors and the like.

[0183] Example

[0184] The present invention will be described below in conjunction with preferred embodiments, but the present invention is not limited to the following embodiments. It should be understood that the attached claims summarize the scope of the present invention. Under the guidance of the concept of the present invention, those skilled in the art should be aware that certain changes made to the various embodiments of the present invention will be covered by the spirit and scope of the claims of the present invention.

[0185] 1. The synthesis method of the organic compound according to the present invention is exemplified, but the present invention is not limited to the following examples.

[0186] Preparation of intermediate 1b:

[0187]

[0188] Under nitrogen protection, add carbazole (30g) and dry tetrahydrofuran solution (500mL) in a three-necked flask, replace with nitrogen three times, add sodium hydride (35g) at low temperature, stir at low temperature for one hour, add 1a (30g), continue stirring at low temperature for one hour, heat under reflux for 6h to stop the reaction, and cool down. Extract with ethyl acetate and deionized water, wash the organic phase twice, dry, filter, and spin-dry the filtrate to obtain 28.1g of crude product of intermediate 1b. Separate by column chromatography (petroleum ether / ethyl acetate 15:1), collect product intermediate 1b to obtain 25.5g. Yield 85%, mass spectrometry analysis determined molecular ion mass 446 (calculated value: 446).

[0189] Preparation of compound 1:

[0190]

[0191] Under nitrogen protection, add 1c (30g), tribromocarbazole (30g), potassium carbonate (25g), tetratriphenylphosphine palladium (1g) and 300mL toluene / 50mL ethanol / 50mL water in a three-necked flask, replace with nitrogen three times, heat to 100℃ for reaction, heat under reflux for 12h to stop the reaction, and cool down. Extract with ethyl acetate and deionized water, wash the organic phase twice, dry, filter, and spin-dry the filtrate to obtain 26g of crude product 1d. Separate by column chromatography (petroleum ether / ethyl acetate 15:1), collect product 1d to obtain 23.2g. Yield 81%, mass spectrometry determined molecular ion mass 500 (calculated value: 500).

[0192] Under nitrogen protection, add 1d (30g) and dry tetrahydrofuran solution (500mL) in a three-necked flask, replace with nitrogen three times, add sodium hydride (35g) at low temperature, stir at low temperature for one hour, add intermediate 1b (30g), continue stirring at low temperature for one hour, heat under reflux for 6h to stop the reaction, and cool down. Extract with ethyl acetate and deionized water, wash the organic phase with water twice, dry, filter, spin dry the filtrate, and obtain 27g of crude product of compound 1. Separate by column chromatography (petroleum ether / ethyl acetate 15:1), collect product compound 1 to obtain 23g. Yield 71%, mass spectrometry analysis determined molecular ion mass 911 (calculated value: 911).

[0193] Preparation of compound 2:

[0194]

[0195] Under nitrogen protection, add 2a (100g), 2b (120g), potassium carbonate (25g), tetratriphenylphosphine palladium (2g) and 3000mL toluene / 500mL ethanol / 500mL water in a three-necked flask, replace with nitrogen three times, heat to 100℃ for reaction, heat under reflux for 12h to stop the reaction, and cool down. Extract with ethyl acetate and deionized water, wash the organic phase twice, dry, filter, and spin-dry the filtrate to obtain 110g of crude product 2c. Separate by column chromatography (petroleum ether / ethyl acetate 15:1), collect product 2c to obtain 108g. Yield 79%, molecular ion mass determined by mass spectrometry is 372 (calculated value: 372).

[0196] Under nitrogen protection, add 2c (30g), dry THF (300mL) in a three-necked flask, replace with nitrogen three times, cool to -78°C with an acetone bath, add 15mL n-butyl lithium solution (n-BuLi, 2.5mol / L n-hexane solution), react at low temperature for 45 minutes, slowly add 30mL of trimethyl borate, continue to react at -78°C for 45 minutes, naturally return to room temperature and stir for 6 hours to stop the reaction. Quench with saturated ammonium chloride aqueous solution, extract with ethyl acetate and deionized water, wash the organic phase twice, recrystallize with petroleum ether, dry, and filter to obtain 25g of crude product 2d. Proceed directly to the next step without treatment.

[0197] Under nitrogen protection, add crude product 2d (30g), tribromocarbazole (35g), potassium carbonate (25g), tetratriphenylphosphine palladium (2g) and 3000mL toluene / 500mL ethanol / 500mL water in a three-necked flask, replace with nitrogen three times, heat to 100℃ for reaction, heat under reflux for 12h to stop the reaction, and cool down. Extract with ethyl acetate and deionized water, wash the organic phase twice, dry, filter, and spin-dry the filtrate to obtain 25g crude product 2e. Separate by column chromatography (petroleum ether / ethyl acetate 15:1), collect product 2e to obtain 23g. Yield 68%, molecular ion mass determined by mass spectrometry 501 (calculated value: 501).

[0198] Under nitrogen protection, add 2e (30 g) and dry tetrahydrofuran solution (500 mL) in a three-necked flask, replace with nitrogen three times, add sodium hydride (35 g) at low temperature, stir at low temperature for one hour, add intermediate 1b (30 g), continue stirring at low temperature for one hour, heat under reflux for 6 hours to stop the reaction, and cool down. Extract with ethyl acetate and deionized water, wash the organic phase twice, dry, filter, spin dry the filtrate, and obtain 20 g of crude product of compound 2. Separate by column chromatography (petroleum ether / ethyl acetate 15:1), collect product compound 2 to obtain 18 g. Yield 65%, mass spectrometry analysis determined molecular ion mass 912 (calculated value: 912).

[0199] Preparation of compound 3:

[0200]

[0201] Under nitrogen protection, add 2a (100g), 3a (120g), potassium carbonate (25g), tetratriphenylphosphine palladium (2g) and 3000mL toluene / 500mL ethanol / 500mL water in a three-necked flask, replace with nitrogen three times, heat to 100℃ for reaction, heat under reflux for 12h to stop the reaction, and cool down. Extract with ethyl acetate and deionized water, wash the organic phase with water twice, dry, filter, and spin-dry the filtrate to obtain 80g of crude product 3b. Separate by column chromatography (petroleum ether / ethyl acetate 15:1), collect product 3b to obtain 75g. Yield 51%, mass spectrometry analysis determined molecular ion mass 396 (calculated value: 396).

[0202] In a dry three-necked flask, add 3b (20g), bipyraclostrobin (15g), potassium acetate (15g), catalyst Pd(dppf)Cl2 (1g) and toluene (300mL), replace with nitrogen three times, heat to 100℃, stir and reflux for 24h, then stop the reaction, separate by column chromatography (petroleum ether / ethyl acetate 25:1), collect product 3c to obtain 6g. Yield 42%, mass spectrometry analysis determined molecular ion mass 381.3 (calculated value: 381.28).

[0203] Under nitrogen protection, add crude product 3c (30g), tribromocarbazole (35g), potassium carbonate (25g), tetratriphenylphosphine palladium (2g) and 3000mL toluene / 500mL ethanol / 500mL water in a three-necked flask, replace with nitrogen three times, heat to 100℃ for reaction, heat under reflux for 12h to stop the reaction, and cool down. Extract with ethyl acetate and deionized water, wash the organic phase twice, dry, filter, and spin-dry the filtrate to obtain 25g of crude product 3d. Separate by column chromatography (petroleum ether / ethyl acetate 15:1), collect product 3d to obtain 23g. Yield 68%, molecular ion mass determined by mass spectrometry 525 (calculated value: 525).

[0204] Under nitrogen protection, add 3d (30g) and dry tetrahydrofuran solution (500mL) in a three-necked flask, replace with nitrogen three times, add sodium hydride (35g) at low temperature, stir at low temperature for one hour, add intermediate 1b (30g), continue stirring at low temperature for one hour, heat under reflux for 6h to stop the reaction, and cool down. Extract with ethyl acetate and deionized water, wash the organic phase twice, dry, filter, spin dry the filtrate, and obtain 20g of crude product of compound 3. Separate by column chromatography (petroleum ether / ethyl acetate 15:1), collect product compound 3 to obtain 18g. Yield 65%, mass spectrometry analysis determined molecular ion mass 912 (calculated value: 912).

[0205] Preparation of compound 4:

[0206]

[0207] Under nitrogen protection, add 2a (100g), 4a (120g), potassium carbonate (25g), tetrakistriphenylphosphine palladium (2g) and 3000mL toluene / 500mL ethanol / 500mL water in a three-necked flask, replace with nitrogen three times, heat to 100℃ for reaction, heat under reflux for 12h to stop the reaction, and cool down. Extract with ethyl acetate and deionized water, wash the organic phase twice, dry, filter, and spin-dry the filtrate to obtain 40g of crude product 4b. Separate by column chromatography (petroleum ether / ethyl acetate 15:1), collect product 4b to obtain 32g. Yield 25%, molecular ion mass determined by mass spectrometry is 523 (calculated value: 523).

[0208] In a dry three-necked flask, add 4b (20g), bipyraclostrobin (15g), potassium acetate (15g), catalyst Pd(dppf)Cl2 (1g) and toluene (300mL), replace with nitrogen three times, heat to 100℃, stir and reflux for 24h, then stop the reaction, separate by column chromatography (petroleum ether / ethyl acetate 25:1), collect product 4c to obtain 2g. Yield 22%, mass spectrometry analysis determined molecular ion mass is 614 (calculated value: 614).

[0209] Under nitrogen protection, add crude product 4c (30g), tribromocarbazole (35g), potassium carbonate (25g), tetrakistriphenylphosphine palladium (2g) and 3000mL toluene / 500mL ethanol / 500mL water in a three-necked flask, replace with nitrogen three times, heat to 100℃ for reaction, heat under reflux for 12h to stop the reaction, and cool down. Extract with ethyl acetate and deionized water, wash the organic phase twice, dry, filter, and spin-dry the filtrate to obtain 5g of crude product 4d. Separate by column chromatography (petroleum ether / ethyl acetate 15:1), collect product 4d to obtain 3g. Yield 21%, mass spectrometry analysis determined molecular ion mass 652 (calculated value: 652).

[0210] Under nitrogen protection, add 4d (30g) and dry tetrahydrofuran solution (500mL) in a three-necked flask, replace with nitrogen three times, add sodium hydride (35g) at low temperature, stir at low temperature for one hour, add intermediate 1b (30g), continue stirring at low temperature for one hour, heat under reflux for 6h to stop the reaction, and cool down. Extract with ethyl acetate and deionized water, wash the organic phase twice, dry, filter, and spin dry the filtrate to obtain 23g of crude product of compound 4. Separate by column chromatography (petroleum ether / ethyl acetate 15:1), collect product compound 4 to obtain 22g. Yield 65%, mass spectrometry analysis determined molecular ion mass 1063 (calculated value: 1063).

[0211] Preparation of compound 5:

[0212]

[0213] Under nitrogen protection, add 2a (100g), 5a (120g), potassium carbonate (25g), tetratriphenylphosphine palladium (2g) and 3000mL toluene / 500mL ethanol / 500mL water in a three-necked flask, replace with nitrogen three times, heat to 100℃ for reaction, heat under reflux for 12h to stop the reaction, and cool down. Extract with ethyl acetate and deionized water, wash the organic phase with water twice, dry, filter, and spin-dry the filtrate to obtain 43g of crude product of compound 5. Separate by column chromatography (petroleum ether / ethyl acetate 15:1), collect product compound 5 to obtain 35g. Yield 41%, mass spectrometry analysis determined molecular ion mass 961 (calculated value: 961).

[0214] Preparation of compound 6:

[0215]

[0216] Under nitrogen protection, add 2a (100g), 6a (120g), potassium carbonate (25g), tetratriphenylphosphine palladium (2g) and 3000ml toluene / 500ml ethanol / 500ml water in a three-necked flask, replace with nitrogen three times, heat to 100℃ for reaction, heat under reflux for 12h to stop the reaction, and cool down. Extract with ethyl acetate and deionized water, wash the organic phase twice, dry, filter, and spin-dry the filtrate to obtain 38g of crude product 6b. Separate by column chromatography (petroleum ether / ethyl acetate 15:1), collect product 6b to obtain 34g. Yield 40%, molecular ion mass determined by mass spectrometry is 461 (calculated value: 461).

[0217] In a dry three-necked flask, add 6b (20g), bipyraclostrobin (15g), potassium acetate (15g), catalyst Pd(dppf)Cl2 (1g) and toluene (300mL), replace with nitrogen three times, heat to 100℃, stir and reflux for 24h, then stop the reaction, separate by column chromatography (petroleum ether / ethyl acetate 25:1), collect product 6c to obtain 11g. Yield 50%, mass spectrometry analysis determined molecular ion mass 552 (calculated value: 552).

[0218] Under nitrogen protection, add crude product 6c (30g), tribromocarbazole (35g), potassium carbonate (25g), tetratriphenylphosphine palladium (2g) and 3000mL toluene / 500mL ethanol / 500mL water in a three-necked flask, replace with nitrogen three times, heat to 100℃ for reaction, heat under reflux for 12h to stop the reaction, and cool down. Extract with ethyl acetate and deionized water, wash the organic phase twice, dry, filter, and spin-dry the filtrate to obtain 10g crude product 6d. Separate by column chromatography (petroleum ether / ethyl acetate 15:1), collect product 6d to obtain 6g. Yield 34%, mass spectrometry analysis determined molecular ion mass 590 (calculated value: 590).

[0219] Under nitrogen protection, add 6d (30 g) and dry tetrahydrofuran solution (500 mL) in a three-necked flask, replace with nitrogen three times, add sodium hydride (35 g) at low temperature, stir at low temperature for one hour, add intermediate 1b (30 g), continue stirring at low temperature for one hour, heat under reflux for 6 hours to stop the reaction, and cool down. Extract with ethyl acetate and deionized water, wash the organic phase twice, dry, filter, spin dry the filtrate, and obtain 25 g of crude product of compound 6. Separate by column chromatography (petroleum ether / ethyl acetate 15:1), collect product compound 6 to obtain 24 g. Yield 70%, mass spectrometry determined molecular ion mass 1001 (calculated value: 1001).

[0220] 2. Energy structure of organic compounds

[0221] The energy levels of organic materials can be obtained by quantum calculation, such as using TD-DFT (time-dependent density functional theory) through Gaussian 09W (Gaussian Inc.), and the specific simulation method can be found in WO2011141110. First, the molecular geometry is optimized using the semi-empirical method "Ground State / Semi-empirical / Default Spin / AM1" (Charge 0 / Spin Singlet), and then the energy structure of the organic molecule is calculated by the TD-DFT (time-dependent density functional theory) method "TD-SCF / DFT / Default Spin / B3PW91" and the basis set "6-31G(d)" (Charge 0 / Spin Singlet). The HOMO and LUMO energy levels are calculated according to the following calibration formula, and S1 and T1 are used directly.

[0222] HOMO(eV)=((HOMO(G)×27.212)-0.9899) / 1.1206

[0223] LUMO(eV)=((LUMO(G)×27.212)-2.0041) / 1.385

[0224] HOMO(G) and LUMO(G) are the direct calculation results of Gaussian 09W, and the unit is Hartree. The results are shown in Table 1:

[0225] Table 1

[0226]

[0227] 3. Preparation and characterization of OLED devices

[0228]

[0229]

[0230] The preparation process of the above-mentioned OLED device is described in detail below through a specific embodiment. The structure of the blue OLED device is: ITO / HI / HT-1 / PH-1 / EML / ET-2 / ET-1:Liq / Liq / Al. The preparation steps of device embodiment 1 are as follows:

[0231] a. Cleaning of ITO (indium tin oxide) conductive glass substrate: Use various solvents (such as one or more of chloroform, acetone or isopropyl alcohol) for cleaning, and then perform ultraviolet ozone treatment.

[0232] b. HI (10 nm), HT-1 (60 nm), HT-2 (5 nm), main material: 10% BD (35 nm), ET-2 (5 nm), ET-1: Liq (50:50; 30 nm), Liq (2 nm), Al (100 nm) in high vacuum (1 × 10 -6 The ITO substrate was moved into a vacuum vapor deposition device and heated in a high vacuum (1×10 -6 mbar), a resistive heating evaporation source is used to form a HI layer with a thickness of 10nm, and a 60nm HT-1 and a 5nm PH-1 layer are heated on the HI layer in sequence. Then, the N-type main body is placed in one evaporation unit, the PH-1 is placed in one evaporation unit, and the compound BD is placed in another evaporation unit as a dopant, and the materials are vaporized at different rates so that the weight ratio of the main body: the dopant is 90:10 (wherein for the case of using two main bodies, the weight ratio of the N-type main body: PH-1: BD is 45:45:10), and a 35nm light-emitting layer is formed on the hole transport layer. Then, a 5nm ET-2 layer is deposited on the light-emitting layer; then, ET-1 and Liq are placed in different evaporation units, and they are co-deposited at a ratio of 50 weight % respectively to form a 30nm electron transport layer, and then 2nm Liq is deposited on the electron transport layer as an electron injection layer, and finally an Al cathode with a thickness of 100nm is deposited on the electron injection layer.

[0233] c. Packaging: The device is packaged with UV-curable resin in a nitrogen glove box.

[0234] The device performance of the above embodiment and comparative example was tested, as shown in Table 2; the current efficiency is 10mA / cm 2 The test is conducted under current density, relative to the value of the comparative example; the device life LT95@1000nits refers to the time it takes for the brightness to decay to 95% when the initial brightness is 1000nits under constant current density, relative to the value of the comparative example.

[0235] The implementation method of device example 2 to device example 12 is the same as that of device example 1, except that different main body and co-main body combinations are used to replace compound 1 (wherein the co-main body refers to two compounds placed in different evaporation units respectively, and the weight ratio of the materials is controlled to be 50:50), and different dopants (BD-1 or BD or BD-3) are used in combination.

[0236] Table 2

[0237]

[0238]

[0239] The performance of blue light OLED device is summarized in the above table 2. After testing, the device performance, especially the life span, is significantly improved by using the organic compound of the present invention and its mixture. It can be seen from the comparison device of ref-1 that it is necessary to introduce tetraphenylsilicon group. Tetraphenylsilicon group can not only increase the steric hindrance of the compound to reduce the quenching effect caused by accumulation in the device, improve the device efficiency, but also can utilize the hyperconjugation effect of Si atom to reduce the triplet energy level of the host compound to a suitable position to match the triplet energy level of the guest. In addition, it can be seen from the comparison with ref-2 that if triphenylsilicon is directly connected to carbazole, the bond energy of carbazole connected to triazine will be reduced, so that the device life span will decrease. Therefore, it is very necessary to introduce a conjugated group on carbazole to reduce the influence of triphenylsilicon on bond energy. It can be seen from the comparison with ref-3 that it is better to introduce tetraphenylsilicon on carbazole than to connect triphenylsilicon directly to triazine, and the main reason is that the influence of triphenylsilicon can be minimized to improve the device efficiency. From ref-4 and ref-5, we can see that the introduction of phenyl groups in blue light devices causes the triplet energy level of the main body to drop too much, which is not suitable for the preparation of blue light devices with low CIEy values. By comparing with ref-6, we can see that the introduction of cyano electron-withdrawing groups on the periphery of carbazole will greatly lower the HOMO energy level of the molecule, making hole injection more difficult, greatly affecting the turn-on voltage and life of the device.

[0240]

[0241] The preparation process of the green light OLED device is described in detail below through a specific embodiment. The structure of the green light OLED device is: ITO / HI / HT-1 / HT-2 / EML / ET-2 / ET-1:Liq / Liq / Al. The preparation steps of device embodiment 13 are as follows:

[0242] a. Cleaning of ITO (indium tin oxide) conductive glass substrate: Use various solvents (such as one or more of chloroform, acetone or isopropyl alcohol) for cleaning, and then perform ultraviolet ozone treatment.

[0243] b. HI (10 nm), HT-1 (50 nm), HT-2 (40 nm), main material: 10% GD (40 nm), ET-2 (5 nm), ET-1: Liq (50:50; 25 nm), Liq (2 nm), Al (100 nm) in high vacuum (1 × 10 -6 The ITO substrate was moved into a vacuum vapor deposition device and heated in a high vacuum (1×10 -6 mbar), a resistive heating evaporation source is used to form a HI layer with a thickness of 10 nm, and a 50 nm HT-1 and a 40 nm HT-2 layer are heated on the HI layer in sequence. Compound 1 is then placed in one evaporation unit, and compound GD is placed in another evaporation unit as a dopant, so that the materials are vaporized at different rates, so that the weight ratio of the main body: compound GD is 90:10, and a 40 nm light-emitting layer is formed on the hole transport layer. ET and Liq are then placed in different evaporation units, and co-deposited at a ratio of 50 weight %, respectively, to form a 30 nm electron transport layer on the light-emitting layer, and then 2 nm Liq is deposited on the electron transport layer as an electron injection layer, and finally a 100 nm thick Al cathode is deposited on the electron injection layer.

[0244] c. Packaging: The device is encapsulated with UV-curable resin in a nitrogen glove box.

[0245] The implementation method of device examples 14 to 17 is the same as that of device example 13, except that compound 1 is replaced by different hosts and different co-hosts (wherein co-host means that two compounds are placed in different evaporation units respectively, and the weight ratio of the deposited materials is controlled by rate setting).

[0246] Table 3

[0247]

[0248] The current voltage and light emission (IVL) characteristics of the green OLED device are characterized by a characterization device, and important parameters such as efficiency and life are recorded. The performance of the green OLED device is summarized in Table 3 above. The lifespan is the value relative to the comparative example. After testing, the device performance, especially the lifespan, is significantly improved by using the organic compound of the present invention and its mixture.

[0249] The above-described embodiments only express several implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for those of ordinary skill in the art, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. An organic compound having a structure as shown in general formula (I): in: Ring A is selected from a substituted or unsubstituted aromatic or heteroaromatic group having 5 to 60 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups; X are independently represented by N or CR1, and at least one X is N; V1 is represented by CR2 or N; V2 is represented by CR3 or N; R1, R2, R3, at each occurrence, may be selected, identically or differently, from H, D, or a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 20 C atoms, or a branched or cyclic alkyl, alkoxy, thioalkoxy or silyl group having 3 to 20 C atoms, or a substituted keto group having 1 to 20 C atoms, or an alkoxycarbonyl group having 2 to 20 C atoms, or an aryloxycarbonyl group having 7 to 20 C atoms, or a cyano group, a carbamoyl group, or a cyclopentyl group. The invention further comprises a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, a haloformyl group, a formyl group, an isocyanate group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a nitro group, a CF3 group, a Cl group, a Br group, a F group, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these groups, wherein one or more of the groups can form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and / or with the ring to which the groups are bonded.

2. The organic compound according to claim 1, characterized in that The organic compound has a structure as shown in one of the general formulas (II-1) to (II-12): Wherein, the definitions of V1, V2, and X are the same as those in claim 1.

3. The organic compound according to claim 2, characterized in that The organic compound has a structure as shown in one of the general formulas (III-1) to (III-12):

4. A polymer comprising at least one repeating unit, characterized in that: The repeating unit comprises at least one structure corresponding to the organic compound according to any one of claims 1 to 3.

5. A mixture comprising a first organic compound (H1) and a second organic compound (H2), wherein the first organic compound (H1) comprises at least one organic compound as described in any one of claims 1 to 3, the second organic compound (H2) has a hole transport property, and the molar ratio of the first organic compound (H1) to the second organic compound (H2) ranges from 1:9 to 9:

1.

6. The mixture according to claim 5, characterized in that The first organic compound (H1) and the second organic compound (H2) have a type II semiconductor heterojunction structure, wherein the first organic compound (H1) comprises a structural unit represented by the general formula (I), and min((LUMO(H1)-HOMO(H2), LUMO(H2)-HOMO(H1))≤min(ET(H1), ET(H2))+0.1eV, wherein LUMO(H1), HOMO(H1) and ET(H1) respectively correspond to the lowest unoccupied orbital, highest occupied orbital and triplet energy level of the first organic compound (H1), and LUMO(H2), HOMO(H2) and ET(H2) respectively correspond to the lowest unoccupied orbital, highest occupied orbital and triplet energy level of the second organic compound (H2).

7. The mixture according to claim 5 or 6, characterized in that The second organic compound (H2) is selected from the general formula (V-1), or a combination of the general formula (V-2) and the general formula (V-3), or any one of the general formula (V-4): wherein G1 and G2 are each independently selected from substituted or unsubstituted aromatic or heteroaromatic groups having 6 to 30 ring atoms; K is independently a single bond or CR at each occurrence 12 R 13 ; s is 0 or 1 independently at each occurrence; Two adjacent * in the general formula (V-2) are connected to two * in the general formula (V-3), and the * in the general formula (V-2) not connected to the general formula (V-3) is independently CR 14 ; L1-L3 are independently selected from substituted or unsubstituted aromatic or heteroaromatic groups having 6 to 30 ring atoms; R4-R 14 The definition is the same as that of R1 in claim 1; Ar1-Ar3 are independently selected from substituted or unsubstituted aromatic groups having 6 to 30 ring atoms or heteroaromatic groups having 2 to 30 ring atoms; n1 is an integer selected from 0 to 7; n2 is selected from an integer from 0 to 8.

8. The mixture according to claim 7, characterized in that The second organic compound (H2) has a structure represented by one of the following general formulas (VI-1) to (VI-10): Among them, G1, G2, K, s, R4-R 11 , L1-L3, Ar1-Ar3, n1, n2 have the same meanings as in claim 7; R 15 The definition is the same as R1 in claim 1.

9. The mixture according to any one of claims 5 to 8, characterized in that The mixture further comprises a light-emitting material, which can be selected from a singlet emitter, a triplet emitter or a TADF material.

10. A composition comprising an organic compound as claimed in any one of claims 1 to 3, or a polymer as claimed in claim 4, or a mixture as claimed in any one of claims 5 to 9, and at least one organic solvent.

11. An organic electronic device, characterized in that: The organic electronic device comprises at least one organic compound according to any one of claims 1 to 3, or a polymer according to claim 4, or a mixture according to any one of claims 5 to 9.

12. The organic electronic device according to claim 11, characterized in that: The organic electronic device is selected from an organic light emitting diode, an organic photovoltaic cell, an organic light emitting cell, an organic field effect transistor, an organic light emitting field effect transistor, an organic laser, an organic spin electronic device, an organic sensor or an organic plasmon emission diode.

13. The organic electronic device according to claim 11, characterized in that: The organic electronic device is an organic electroluminescent device and comprises a light-emitting layer, wherein the light-emitting layer comprises at least one organic compound according to any one of claims 1 to 3, or a polymer according to claim 4, or a mixture according to any one of claims 5 to 9.

14. The organic electronic device according to claim 11, characterized in that: The organic electronic device is an organic electroluminescent device and comprises an electron transport layer or a hole blocking layer, wherein the electron transport layer or the hole blocking layer comprises at least one organic compound according to any one of claims 1 to 3.

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