Organic mixture, organic compound, and use thereof in organic electronic device

Abstract

Disclosed in the present invention is an organic mixture, comprising a first compound H1 and a second compound H2, wherein the first compound H1 is a p-type material with bicarbazole as a core structure, and the second compound H2 is an n-type material with biindolyl[3,21-jk]carbazole as a core structure. Further disclosed is an organic compound. The organic compound has a relatively high thermal stability. When used to prepare a light-emitting device, the organic compound can reduce the voltage of the device and improve the efficiency of the device. Further disclosed is an organic compound. The organic compound has a relatively high thermal stability. When used to prepare a light-emitting device, the organic compound can reduce the voltage of the device and improve the efficiency of the device. The present invention further relates to a printing ink comprising the organic mixture. The present invention further relates to an organic compound with biindolyl[3,21-jk]carbazole as a core structure, and the use thereof in an organic electronic device.

Description

An organic mixture, an organic compound and their application in organic electronic devices Technical Field

[0001] The present invention relates to an organic mixture, an organic compound, a composition containing the same and an optoelectronic device. The present invention also relates to an electronic device containing the organic mixture or organic compound and applications thereof, in particular, applications in electroluminescent devices. Background Art

[0002] Organic light-emitting diodes (OLEDs) are considered by the industry to be the most promising next-generation display and lighting technology due to their lightweight, active luminescence, high color purity, wide viewing angle, high contrast, high luminous efficiency, low energy consumption, and ease of fabrication for flexible and large-scale panels. To promote the large-scale industrialization of OLEDs, further improving their luminous performance and lifespan is a key challenge that needs to be addressed. The development of high-performance organic optoelectronic materials is crucial to addressing this issue.

[0003] Organic light-emitting diodes (OLEDs) are electroluminescent devices that convert electrical energy into light. To further improve the luminous efficiency of OLEDs, it is necessary to maximize energy conversion efficiency and minimize energy loss. For electroluminescent devices, according to the statistical laws of electron spin in quantum mechanics, singlet and triplet excitons are generated in a ratio of 1:3. This results in a maximum energy utilization rate (internal quantum efficiency) of only 25% for conventional fluorescent materials. However, phosphorescent materials, due to the heavy atom effect, enhance spin-orbit coupling in the triplet state, enabling the previously spin-forbidden transition from the triplet state to the ground state. Both singlet and triplet excitons can radiate light, and the energy utilization rate can theoretically reach 100%. Currently, significant progress has been made in red and green phosphorescent materials, both in terms of host and guest properties, leading to industrialization. However, the performance of phosphorescent blue OLEDs, particularly their lifetime, remains far below commercial standards, forcing the use of fluorescent blue OLEDs in current commercial displays. Due to their low efficiency, fluorescent blue OLEDs are the primary limiting factor in OLED display energy consumption. Blue phosphorescent materials have become the last holy grail of OLED materials.

[0004] Blue phosphorescent OLEDs depend on the host and guest materials. The host material can achieve a balance between energy level matching and charge transfer, preventing exciton aggregation quenching, and is an indispensable component for improving the device lifespan and stability of organic light-emitting diodes. Using exciplexes as phosphorescent host materials is a relatively common method. This method can use two organic compounds of different polarities to form an intermediate state, namely an exciplex, to improve the device lifespan (see, for example, Kim et al., Adv. Mater., Vol 26, 5864, (2014)). To date, many companies have reported technologies using exciplexes as co-hosts. For example, Rohm and Haas Electronic Materials Korea Ltd. disclosed a co-host in which the first host and the second host are a bicarbazole derivative and a carbazole derivative, respectively (US2017 / 0062730). Samsung disclosed a co-host in which the two host materials are selected from an electron transport host and a hole transport host, respectively (KR20160026744). Recently, Sun et al. reported a blue phosphorescent device (DOI: 10.1038 / s41566-022-00958-4) that achieved a significant breakthrough in lifetime. The device utilizes SiCzCz as a p-type host and SiTrzCz2 as an n-type host, effectively forming an exciplex. However, its lifetime still falls short of commercialization requirements.

[0005] Therefore, more stable host materials still need to be developed. Summary of the Invention

[0006] In view of the above-mentioned deficiencies in the prior art, the object of the present invention is to provide an organic mixture, namely a co-host material, comprising a first compound H1 and a second compound H2, wherein the first compound H1 is a p-type material with biindole [3,21-jk] carbazole as the core structure, and the second compound H2 is an n-type material with biindole [3,21-jk] carbazole as the core structure, and an organic compound with biindole [3,21-jk] carbazole as the core structure, aiming to solve the problems of low stability and device life of existing organic electronic devices.

[0007] The technical solutions of the present invention are as follows:

[0008] An organic mixture comprises a first compound H1 and a second compound H2, wherein the first compound H1 is selected from chemical formula (I-1) or (I-2), and the second compound H2 is selected from chemical formula (II-1):

[0009] Ar1-Ar3 are selected from substituted or unsubstituted aromatic or heteroaromatic groups having 5 to 40 ring atoms, or aryloxy or heteroaryloxy groups having 5 to 40 ring atoms, or combinations of these groups, wherein one or more of these groups can form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and / or with the ring to which they are bonded;

[0010] L is a divalent bridging group selected from a substituted or unsubstituted aromatic group or heteroaromatic group having 5 to 20 ring atoms, and the bond connecting L to the two indole[3,21-jk]carbazoles is not a CN bond;

[0011] R1-R6 are substituents which, at each occurrence, may be identical or different and are selected from D, or linear alkyl, alkoxy or thioalkoxy groups having 1 to 20 carbon atoms, or branched or cyclic alkyl, alkoxy, thioalkoxy or silyl groups having 3 to 20 carbon atoms, or keto groups having 1 to 20 carbon atoms, or alkoxycarbonyl groups having 2 to 20 carbon atoms, or aryloxycarbonyl groups having 7 to 20 carbon atoms, or cyano, carbamoyl, haloformyl, formyl, isocyanate, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, CF3, Cl, Br, F, 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;

[0012] n1, n3, n4 are integers selected from 0 to 7;

[0013] n2 is an integer selected from 0 to 8;

[0014] n5 and n6 are selected from integers from 0 to 10.

[0015] Preferably, in the organic mixture, the first compound H1 and the second compound H2 form a type II heterojunction structure, and min(LUMO(H1)-HOMO(H2),LUMO(H2)-HOMO(H1))≤min(E T1 (H1),E T1 (H2))+0.1eV, where HOMO(H1), LUMO(H1) and E T1 (H1) are the highest occupied molecular orbital, lowest unoccupied molecular orbital, and triplet energy level of the first compound H1; HOMO(H2), LUMO(H2) and E T1 (H2) are the highest occupied molecular orbital, lowest unoccupied molecular orbital, and triplet energy level of H2 of the second compound, respectively.

[0016] The organic mixture further comprises another organic functional material; the another organic functional material is preferably a self-luminous body, and the luminous body is preferably a self-fluorescent luminous body, a phosphorescent luminous body or a TADF material.

[0017] The present invention also relates to a composition comprising an organic mixture as described above and at least one organic solvent.

[0018] The present invention further relates to an organic compound having a structure represented by chemical formula (II-1), characterized in that: L does not contain a cyano group, and L is selected from the following electron-withdrawing groups, which may be further substituted:

[0019] Among them, X 1 -X 8 Selected from CR or N, and at least one of them is N; Z1, Z2, and Z3 independently represent N(R), C(R)2, Si(R)2, O, C=N(R), C=C(R)2, P(R), P(=O)R, S, S=O, SO2 or none, but at least one of them is not none; wherein R can be selected from the following groups: hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl.

[0020] The present invention further relates to a photovoltaic device comprising an organic mixture or organic compound as described above.

[0021] Beneficial Effects: The organic mixture or organic compound according to the present invention, when applied to organic electronic devices, such as electroluminescent devices, can provide high luminous efficiency and device life. This may be due to, but not limited to, the following: the indole[3,21-jk]carbazole core structure contained in the second compound H2 is an n-type structure with a large delocalized frontier electron orbital. Furthermore, compared to the CN bond in SiTrzCz2, the C-C bond connecting the indole[3,21-jk]carbazole core structure to other groups has a larger dissociation energy; thus, the device life and stability can be improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 is a diagram of a heterojunction structure, showing two possible types of relative positions of the energy levels of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) when two organic semiconductor materials H1 and H2 are in contact, among which the type II semiconductor heterojunction structure is the energy level structure of the organic mixture according to the present invention. DETAILED DESCRIPTION

[0023] The present invention provides an organic mixture, namely a co-host material, comprising two compounds, a first compound H1 and a second compound H2. The first compound H1 is a p-type material with a bicarbazole core structure, and the second compound H2 is an n-type material with a biindole[3,21-jk]carbazole core structure. Furthermore, an organic compound with a biindole[3,21-jk]carbazole core structure is provided. To further clarify the objectives, technical solutions, and effects of the present invention, the present invention is described in further detail below. It should be understood that the specific embodiments described herein are intended only to illustrate the present invention and are not intended to limit the present invention.

[0024] In the description of the embodiments of the present invention, a numerical range represented by “~” refers to a range that includes the numerical values ​​described before and after “~” as the lower limit and the upper limit.

[0025] In this disclosure, the term "and / or" describes the relationship between associated objects, indicating that three possible relationships exist. For example, "A and / or B" can represent: A exists alone, A and B exist simultaneously, and B exists alone. A and B can be singular or plural. The character " / " generally indicates that the associated objects are in an "or" relationship.

[0026] In the present invention, "at least one" means one or more, and "plurality" means two or more. "At least one of the following" or similar expressions refers to any combination of these items, including any combination of single items or plural items. For example, "at least one of a, b, or c" or "at least one of a, b, and c" can all mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can each be single or plural.

[0027] It should be understood that in various embodiments of the present invention, the size of the serial number of each process does not mean the order of execution. Some or all steps can be executed in parallel or sequentially. The execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present invention.

[0028] The terms used in the embodiments of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention. The singular forms "a", "an", "the" and "the" used in the embodiments of the present invention and the appended claims are also intended to include plural forms unless the context clearly indicates otherwise.

[0029] The term "OLED" is an abbreviation for "Organic Light Emitting Diode," which stands for organic electroluminescent diode, also known as organic electric laser display or organic light-emitting semiconductor (Organic Electroluminescence Display, OLED). OLED is a current-type organic light-emitting device that emits light through the injection and recombination of carriers, and the luminous intensity is proportional to the injected current. Under the action of the electric field, the holes generated by the anode and the electrons generated by the cathode will move, and are injected into the hole transport layer and the electron transport layer respectively, and migrate to the light-emitting layer. When the two meet in the light-emitting layer, energy excitons are generated, which excite the light-emitting molecules and ultimately produce visible light.

[0030] The term "TADF," short for "Thermally Activated Delayed Fluorescence," refers to thermally activated delayed fluorescence, which occurs when the triplet excited state and singlet excited state are close in energy, allowing the triplet excited state to transition to the singlet excited state through thermally activated reverse intersystem crossing (ISC). Conventional luminescence occurs as fluorescence and phosphorescence, respectively, where the exciton returns to the ground state via radiative emission from the singlet and triplet states. Furthermore, the energy difference between the lower singlet and triplet states is typically large, resulting in an inability to return the exciton to the singlet state once it reaches the triplet state through ISC.

[0031] In the present invention, main material, matrix material, host or matrix material have the same meaning and can be interchanged.

[0032] In the present invention, metal organic complex, metal organic complex and organometallic complex have the same meaning and can be used interchangeably.

[0033] In the present invention, the term "substituted or unsubstituted" means that a hydrogen atom in the compound is replaced by a substituent, and "unsubstituted" means that a hydrogen atom on the group is not replaced by a substituent. The substituent may be selected from the following groups: D, F, CN, alkenyl, alkynyl, amine, nitro, acyl, alkoxy, carbonyl, sulfone, boron-containing group, silicon-containing group, alkyl group having 1 to 50 carbon atoms (preferably 1 to 18, more preferably 1 to 8), cycloalkyl group having 3 to 50 ring atoms (preferably 3 to 10, more preferably 3 to 8, and even more preferably 5 or 6), aromatic hydrocarbon group or aromatic heterocyclic group having 3 to 50 ring atoms (preferably 3 to 25, more preferably 3 to 18).

[0034] In the present invention, the "number of ring atoms" refers to the number of atoms in the atoms that constitute the ring itself of a structural compound (e.g., a monocyclic compound, a condensed ring compound, a cross-linked compound, a carbocyclic compound, or a heterocyclic compound) formed by atoms bonded together to form a ring. When the ring is substituted with a substituent, the atoms contained in the substituent are not included in the ring atoms. The "number of ring atoms" described below also applies unless otherwise specified. For example, the number of ring atoms of a benzene ring is 6, the number of ring atoms of a naphthalene ring is 10, and the number of ring atoms of a thienyl group is 5.

[0035] For purposes of the present invention, an "aromatic hydrocarbon group" refers to a hydrocarbon group containing at least one aromatic ring, including monocyclic and polycyclic ring systems. An "aromatic heterocyclic group" refers to a hydrocarbon group containing at least one aromatic heterocyclic ring (containing heteroatoms), including monocyclic and polycyclic ring systems. These polycyclic rings may have two or more rings in which two carbon atoms are shared by two adjacent rings, i.e., a fused ring. At least one of these polycyclic rings is aromatic or heteroaromatic. For the purposes of the present invention, an aromatic or heteroaromatic ring system includes not only systems containing aromatic or heteroaromatic groups, but also systems in which multiple aromatic or heteroaromatic groups are interrupted by short non-aromatic units (<10% non-H atoms, preferably less than 5% non-H atoms, such as C, N, or O atoms). Thus, systems such as 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamines, and diaryl ethers are also considered aromatic ring systems for the purposes of this invention.

[0036] Specific examples of the aromatic hydrocarbon group include benzene, naphthalene, anthracene, phenanthrene, perylene, tetracene, pyrene, benzopyrene, triphenylene, acenaphthene, fluorene, and derivatives thereof.

[0037] Specific examples of aromatic heterocyclic groups include furan, benzofuran, thiophene, benzothiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, indole, carbazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furopyrrole, furofuran, thienofuran, benzisoxazole, benzisothiazole, benzimidazole, pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, o-naphthylidene, quinoxaline, phenanthridine, primary idine, quinazoline, quinazolinone, and derivatives thereof.

[0038] In the embodiment of the present invention, the energy level structure of the organic material, the singlet energy level E S1 , triplet energy level E T1 , HOMO, and LUMO play a key role. The following is an introduction to the determination of these energy levels.

[0039] 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 (CV). Recently, quantum chemical methods, such as density functional theory (DFT), have also become effective methods for calculating molecular orbital energy levels.

[0040] The singlet energy level E of organic materials S1 It can be measured by fluorescence luminescence spectrum at room temperature or low temperature; the triplet energy level E T1 It can be measured by low-temperature time-resolved luminescence spectroscopy; or obtained by quantum simulation calculation (such as by Time-dependent DFT), such as by the commercial software Gaussian 09W (Gaussian Inc.). The specific simulation method can be found in WO2011141110 or as described below in the examples.

[0041] 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. 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.

[0042] In the present invention, (HOMO-1) is defined as the second-highest occupied molecular orbital energy level, (HOMO-2) is the third-highest occupied molecular orbital energy level, and so on. (LUMO+1) is defined as the second-lowest unoccupied molecular orbital energy level, (LUMO+2) is the third-lowest occupied molecular orbital energy level, and so on.

[0043] The present invention provides an organic mixture comprising a first compound H1 and a second compound H2, wherein the first compound H1 is selected from chemical formula (I-1) or (I-2), and the second compound H2 is selected from chemical formula (II-1):

[0044] Ar1-Ar3 are selected from substituted or unsubstituted aromatic or heteroaromatic groups having 5 to 40 ring atoms, or aryloxy or heteroaryloxy groups having 5 to 40 ring atoms, or combinations of these groups, wherein one or more of these groups can form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and / or with the ring to which they are bonded;

[0045] L is a divalent bridging group selected from substituted or unsubstituted aromatic or heteroaromatic groups having 5 to 20 ring atoms, and the bond connecting L to the two indolo[3,21-jk]carbazoles is not a CN bond. When either of the two indolo[3,21-jk]carbazoles is connected to L by a CN bond, the BDE (bond dissociation energy) of CN is very low in the case of negative charge. Therefore, for the purposes of the present invention, the second compound H2 is an n-type material, wherein the bond connecting L to the indolo[3,21-jk]carbazole excludes CN.

[0046] R1-R6 are substituents which, at each occurrence, may be identical or different and are selected from D, or linear alkyl, alkoxy or thioalkoxy groups having 1 to 20 carbon atoms, or branched or cyclic alkyl, alkoxy, thioalkoxy or silyl groups having 3 to 20 carbon atoms, or keto groups having 1 to 20 carbon atoms, or alkoxycarbonyl groups having 2 to 20 carbon atoms, or aryloxycarbonyl groups having 7 to 20 carbon atoms, or cyano, carbamoyl, haloformyl, formyl, isocyanate, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, CF3, Cl, Br, F, 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;

[0047] n1, n3, and n4 are selected from integers from 0 to 7; n2 is selected from integers from 0 to 8; and n5 and n6 are selected from integers from 0 to 10.

[0048] In a preferred embodiment, the organic mixture, wherein the first compound H1 and the second compound H2 form a type II heterojunction structure, i.e., the highest occupied molecular orbital energy level (HOMO) (H1) of the first compound H1 is higher than the HOMO (H2) of the second compound H2, and the lowest unoccupied molecular orbital energy level (LUMO) (H1) of the first compound H1 is higher than the LUMO (H2) of the second compound H2. In certain embodiments, the energy gap of the first compound H1 is smaller than that of the second compound H2. In certain more preferred embodiments, the energy gap of the first compound H1 is larger than that of the second compound H2.

[0049] In certain embodiments, for the organic mixture, HOMO(H1)≥HOMO(H2)+0.10 eV, and / or LUMO(H1)≥LUMO(H2)+0.10 eV.

[0050] In a more preferred embodiment, for the organic mixture, HOMO(H1)≥HOMO(H2)+0.20 eV, and / or LUMO(H1)≥LUMO(H2)+0.20 eV.

[0051] In a more preferred embodiment, for the organic mixture, HOMO(H1)≥HOMO(H2)+0.25eV, and / or LUMO(H1)≥LUMO(H2)+0.25eV.

[0052] In a most preferred embodiment, for the organic mixture, HOMO(H1)≥HOMO(H2)+0.30 eV, and / or LUMO(H1)≥LUMO(H2)+0.30 eV.

[0053] In certain embodiments, the first compound H1 and the second compound H2, wherein E ex =min(LUMO(H1)-HOMO(H2),LUMO(H2)-HOMO(H1))≤min(E T1 (H1),E T1 (H2))+0.2eV, where HOMO(H1), LUMO(H1) and E T1 (H1) are the highest occupied molecular orbital, lowest unoccupied molecular orbital, and triplet energy level of the first compound H1; HOMO(H2), LUMO(H2) and E T1 (H2) are the highest occupied molecular orbital, lowest unoccupied molecular orbital, and triplet energy level of H2 of the second compound, respectively.

[0054] In a more preferred embodiment, E ex ≤min(E T1 (H1),E T1 (H2))+0.1eV, better is E ex ≤min(E T1 (H1),E T1 (H2)), particularly preferably ≤min(E T1 (H1),E T1 (H2))-0.1eV, the best is ≤min(E T1 (H1),E T1 (H2))-0.2eV.

[0055] In certain embodiments, E ex ≥2.6eV, preferably E ex ≥2.7eV, preferably E ex ≥2.75eV, the best is E ex ≥2.8eV.

[0056] In a preferred embodiment, the exciplex formed between the first compound H1 and the second compound H2 has a singlet energy level E S1 and triplet energy level E T1 The difference is ≤0.3 eV, preferably ≤0.25 eV, more preferably ≤0.2 eV, particularly preferably ≤0.15 eV.

[0057] In a more preferred embodiment, the first compound H1 is selected from any one of chemical formulas (I-1a), (I-1b) or (I-2a):

[0058] In a particularly preferred embodiment, the first compound H1 is selected from the chemical formula (I-1a) or (I-2a).

[0059] In certain preferred embodiments, the above-mentioned Ar1, Ar2, and Ar3 are independently represented by substituted or unsubstituted aromatic groups or aromatic hetero groups with 5 to 30 ring atoms; in more preferred embodiments, Ar1, Ar2, and Ar3 are independently represented by substituted or unsubstituted aromatic groups or aromatic hetero groups with 5 to 20 ring atoms; in the most preferred embodiment, Ar1, Ar2, and Ar3 are independently represented by substituted or unsubstituted aromatic groups or aromatic hetero groups with 5 to 15 ring atoms.

[0060] In some preferred embodiments, the above-mentioned Ar1, Ar2, and Ar3 may comprise one or more combinations of the following structural groups:

[0061] Among them, A 1 、A 2 、A 3 、A 4 、A 5 、A 6 、A 7 、A 8 Each independently represents CR 7 or N; W 1 、W 2 Independently selected from CR 8 R 9 、SiR 8 R 9 NR 7 , C(=O), S or O;

[0062] R 7 、R 8 、R 9The radicals may be selected, at each occurrence, identically or differently, from H, D, or straight-chain alkyl, alkoxy or thioalkoxy radicals having 1 to 20 C atoms, or branched or cyclic alkyl, alkoxy, thioalkoxy or silyl radicals having 3 to 20 C atoms, or keto radicals having 1 to 20 C atoms, or alkoxycarbonyl radicals having 2 to 20 C atoms, or aryloxycarbonyl radicals having 7 to 20 C atoms, or cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, CF3, Cl, Br, F, 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 radicals, where one or more of the radicals can form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and / or the ring to which the radicals are bonded.

[0063] In a more preferred embodiment, the above-mentioned Ar1, Ar2, and Ar3 comprise one of the following structural groups, wherein the H on the ring can be arbitrarily substituted:

[0064] Furthermore, the above-mentioned Ar1, Ar2, and Ar3 are selected from benzene, biphenyl, naphthalene, anthracene, phenanthrene, pyrene, pyridine, pyrimidine, triazine, fluorene, dibenzothiazolidine, silylation, carbazole, thiophene, furan, thiazole, triphenylamine, triphenylphosphine, tetraphenylsilane, spirofluorene, spirosilicon fluorene and other groups and any combination thereof; more preferably, benzene, biphenyl, pyridine, pyrimidine, triazine, furan, carbazole and other groups and any combination thereof.

[0065] In a preferred embodiment, Ar2 or Ar3 in Formula (I-2) or Formula (I-2a) contains an electron-withdrawing group, in particular a weak electron-withdrawing group, preferably pyridine, pyrimidine and pyrazine.

[0066] In a more preferred embodiment, n1, n3, and n4 are 0, that is, there is no corresponding substitution.

[0067] In certain preferred embodiments, the substituents R1-R6 are independently selected from H, D, CN, substituted or unsubstituted alkyl groups with 1 to 18 carbon atoms, substituted or unsubstituted cycloalkyl groups with 3 to 18 carbon atoms, substituted or unsubstituted aromatic hydrocarbon groups or aromatic heterocyclic groups with 5 to 30 ring atoms; in more preferred embodiments, R1-R6 are independently H, D, substituted or unsubstituted alkyl groups with 1 to 12 carbon atoms, substituted or unsubstituted aromatic hydrocarbon groups or aromatic heterocyclic groups with 5 to 20 ring atoms; in the most preferred embodiment, R1-R6 are independently H, D, substituted or unsubstituted alkyl groups with 1 to 6 carbon atoms, substituted or unsubstituted aromatic hydrocarbon groups or aromatic heterocyclic groups with 5 to 15 ring atoms.

[0068] In certain embodiments, E T1 (H1) ≥ 2.7 eV, preferably ≥ 2.8 eV, more preferably ≥ 2.85 eV, most preferably ≥ 2.9 eV.

[0069] Preferred examples of the first compound H1 according to the chemical formula (I-1), (I-1a), (I-1b), (I-2) and (I-2a) are shown below, but are not limited to:

[0070] According to the second compound H2 of chemical formula (II-1), its core is composed of two indole[3,21-jk]carbazoles connected by a divalent linking group L, and the connection method can be arbitrary.

[0071] In certain preferred embodiments, in the aforementioned linkage method, the linkage position of the divalent linking group L is selected from (2, 5, 10) of the first indole[3,21-jk]carbazole and (2', 5', 10') of the second indole[3,21-jk]carbazole:

[0072] In some preferred embodiments, the second compound H2 is selected from any one of chemical formulas (II-1a) to (II-1e):

[0073] In certain more preferred embodiments, the H2 is selected from chemical formulas (II-1a) to (II-1c).

[0074] In a preferred embodiment, L is a divalent bridging group selected from a substituted or unsubstituted aromatic group or heteroaromatic group having 5 to 20 ring atoms; more preferably, a substituted or unsubstituted aromatic group or heteroaromatic group having 5 to 15 ring atoms; particularly preferably, a substituted or unsubstituted aromatic group or heteroaromatic group having 5 to 13 ring atoms.

[0075] In a more preferred embodiment, according to the organic mixture of the present invention, L in the chemical formula (II-1) and chemical formulas (II-1a) to (II-1e) contains an electron-withdrawing group.

[0076] Examples of suitable groups having electron-withdrawing properties are shown below, but are not limited thereto, which may be further substituted optionally:

[0077] wherein n is selected from an integer from 1 to 3; X 1 -X 8is selected from CR or N, and at least one of them is N, Z1, Z2, and Z3 independently represent N(R), C(R)2, Si(R)2, O, C=N(R), C=C(R)2, P(R), P(=O)R, S, S=O, SO2 or none, but at least one of them is not none; wherein R can be selected from the following groups: hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl.

[0078] Further electron withdrawing groups may be selected from structures comprising the following groups, which may be further optionally substituted:

[0079] In some particularly preferred embodiments, the electron-withdrawing group is selected from CN or one or more combinations of the structures shown below:

[0080] In a more preferred embodiment, according to the organic mixture of the present invention, wherein, in the chemical formula (II-1) and chemical formula (II-1a)-(II-1e), n5+n6≥1, and at least one of R5 or R6 contains an electron-withdrawing group.

[0081] In a preferred embodiment, L does not contain a cyano group.

[0082] In some other preferred embodiments, according to the organic mixture of the present invention, the second compound H2 is selected from the chemical formula (II-1a-1) to (II-1e-1):

[0083] Among them, Ar a1 -Ar a4 ,Ar b1 -Ar b4 ,Ar c1 -Ar c4 ,Ar d1 -Ar d4 ,Ar e1 -Ar e4 Each of the groups is independently selected from H, D, F, cyano, and a substituted or unsubstituted aromatic group or aromatic hetero group having 5 to 30 ring atoms.

[0084] In a particularly preferred embodiment, Ar a1 -Ar a4 ,Ar b1 -Ar b4 ,Ar c1 -Ar c4 ,Ar d1 -Ar d4 ,Ar e1 -Ar e4All are selected from H or D.

[0085] In other preferred embodiments, Ar a1 -Ar a4 ,Ar b1 -Ar b4 ,Ar c1 -Ar c4 ,Ar d1 -Ar d4 ,Ar e1 -Ar e4 is selected from substituted or unsubstituted aromatic groups or heteroaromatic groups having 5 to 20 ring atoms; more preferably, substituted or unsubstituted aromatic groups or heteroaromatic groups having 5 to 15 ring atoms; particularly preferably, substituted or unsubstituted aromatic groups or heteroaromatic groups having 5 to 13 ring atoms; most preferably, substituted or unsubstituted aromatic groups or heteroaromatic groups having 5 to 9 ring atoms.

[0086] In certain embodiments, Ar a1 -Ar a4 ,Ar b1 -Ar b4 ,Ar c1 -Ar c4 ,Ar d1 -Ar d4 ,Ar e1 -Ar e4 Selected from benzene, biphenyl, pyridine, pyrimidine, triazine, furan, carbazole and any combination thereof.

[0087] In certain preferred embodiments, Ar a1 -Ar a4 At least one of them contains the above electron-withdrawing group; Ar b1 -Ar b4 At least one of them contains the above electron-withdrawing group; Ar c1 -Ar c4 At least one of them contains the above electron-withdrawing group; Ar d1 -Ar d4 At least one of them contains the above electron-withdrawing group; Ar e1 -Ar e4 At least one of them contains the above-mentioned electron-withdrawing group.

[0088] In some preferred embodiments, Ar a1 -Ar a4 At least one of them contains a weak electron-withdrawing group; Ar b1 -Ar b4 At least one of them contains a weak electron-withdrawing group; Ar c1 -Arc4 At least one of them contains the weak electron-withdrawing group mentioned above; Ar d1 -Ar d4 At least one of them contains a weak electron-withdrawing group; Ar e1 -Ar e4 At least one of the groups contains a weak electron-withdrawing group. The weak electron-withdrawing group is preferably selected from the following groups:

[0089] In certain embodiments, E T1 (H2) ≥ 2.65 eV, preferably ≥ 2.7 eV, more preferably ≥ 2.75 eV, most preferably ≥ 2.85 eV.

[0090] In certain embodiments, the above-mentioned Ar1-Ar3, R5, R6, Ar a1 -Ar a4 ,Ar b1 -Ar b4 ,Ar c1 -Ar c4 ,Ar d1 -Ar d4 ,Ar e1 -Ar e4 Can be further selected from the following chemical formula (A):

[0091] Wherein L0 is selected from a single bond or any divalent linking group; the dotted line represents the linking bond; Ar7-Ar9 are selected from a substituted or unsubstituted aromatic group or heteroaromatic group having 5 to 30 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 30 ring atoms, or a combination of these groups; preferably a substituted or unsubstituted aromatic group or heteroaromatic group having 5 to 20 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 20 ring atoms, or a combination of these groups; more preferably a substituted or unsubstituted aromatic group or heteroaromatic group having 5 to 15 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 15 ring atoms, or a combination of these groups.

[0092] In a more preferred embodiment, Ar7-Ar9 are selected from benzene, biphenyl, pyridine, pyrimidine, triazine, furan, carbazole or indolecarbazole; particularly preferably benzene, biphenyl, pyridine, pyrimidine, triazine or furan.

[0093] Preferred examples of the second compound H2 according to formula (II-1), formula (II-1a)-(II-1e) and formula (II-1a-1)-(II-1e-1) are shown below, but are not limited to:

[0094] In a very preferred embodiment, the organic mixture is used for the light-emitting layer of an organic electroluminescent device. In some embodiments, due to stability or process considerations, there may be some special requirements for the first compound H1 and the second compound H2.

[0095] In a preferred embodiment, according to the organic mixture of the present invention, at least one of the first compound H1 and the second compound H2 has ((LUMO+1)-LUMO) ≥ 0.1eV, preferably ≥ 0.15eV, better ≥ 0.20eV, even better ≥ 0.25eV, and most preferably ≥ 0.30eV.

[0096] In a more preferred embodiment, according to the organic mixture of the present invention, the second compound H2 has ((LUMO+1)-LUMO) ≥ 0.1eV, preferably ≥ 0.15eV, better ≥ 0.20eV, even better ≥ 0.25eV, and most preferably ≥ 0.30eV.

[0097] In another preferred embodiment, according to the organic mixture of the present invention, at least one of the first compound H1 and the second compound H2 has a (HOMO-(HOMO-1)) ≥ 0.2 eV, preferably ≥ 0.25 eV, more preferably ≥ 0.30 eV, even better ≥ 0.35 eV, and most preferably ≥ 0.40 eV.

[0098] In another more preferred embodiment, according to the organic mixture of the present invention, the first compound H1 has (HOMO-(HOMO-1)) ≥ 0.2eV, preferably ≥ 0.25eV, better ≥ 0.30eV, even better ≥ 0.35eV, and most preferably ≥ 0.40eV.

[0099] In a preferred embodiment, in the organic mixture, the molar ratio of the first compound H1 to the second compound H2 is from 2:8 to 8:2; the preferred molar ratio is 3:7 to 7:3; and the more preferred molar ratio is 4:6 to 6:4.

[0100] In a preferred embodiment, at least one of the first compound H1 and the second compound H2 in the organic mixture of the present invention 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 a further more preferred embodiment, at least one has a Tg ≥ 160°C; in a most preferred embodiment, at least one has a Tg ≥ 180°C.

[0101] In a more preferred embodiment, at least one of the first compound H1 and the second compound H2 in the organic mixture according to the present invention is partially H-deuterated, preferably ≥10% H-deuterated, more preferably ≥20% H-deuterated, most preferably ≥30% H-deuterated, and most preferably ≥40% H-deuterated.

[0102] In a preferred embodiment, in the organic mixture according to the present invention, both the first compound H1 and the second compound H2 are small molecule materials.

[0103] One object of the present invention is to provide a material solution for vapor deposition type OLEDs.

[0104] In a preferred embodiment, the organic mixture according to the present invention is used in an evaporation-type OLED device. For this purpose, the molecular weight of the first compound H1 and the second compound H2 in the organic mixture material according to the present invention is ≤1000 g / mol, preferably ≤900 g / mol, more preferably ≤850 g / mol, even more preferably ≤800 g / mol, and most preferably ≤700 g / mol.

[0105] The following are more important preferred embodiments:

[0106] Embodiment I: The organic mixture, wherein the difference in molecular weight between the first compound H1 and the second compound H2 does not exceed 80 Dalton; preferably, the difference in molecular weight does not exceed 60 Dalton; more preferably, the difference in molecular weight does not exceed 30 Dalton.

[0107] Embodiment II: The organic mixture, wherein the difference in sublimation temperature between the first compound H1 and the second compound H2 is no more than 30K; preferably, the difference in sublimation temperature is no more than 20K; more preferably, the difference in sublimation temperature is no more than 10K.

[0108] Example III: The organic mixture, wherein the difference in evaporation rate between the first compound H1 and the second compound H2 at a certain vacuum degree and a certain evaporation temperature does not exceed 5% (based on the evaporation rate of the first compound H1), more preferably does not exceed 4%, and most preferably does not exceed 3%.

[0109] The present invention also relates to an organic mixture, in particular to a preparation method (premix preparation method) according to Example I and / or Example II and / or Example III: a first compound H1 and a second compound H2 in a certain mass ratio are mixed as uniformly as possible, and then the mixture is placed in a temperature less than or equal to 10 -3 In a vacuum environment of Torr, the temperature in the vacuum environment is increased to completely melt the two main materials, and after being mixed evenly, the mixture is cooled to room temperature to solidify, and then ground into powder using a ball mill for standby use.

[0110] Another object of the present invention is to provide a material solution for printed OLEDs.

[0111] For this purpose, at least one, preferably both, of the first compound H1 and the second compound H2 in the organic mixture according to the invention have a molecular weight of ≥700 g / mol, preferably ≥800 g / mol, more preferably ≥900 g / mol, even more preferably ≥1000 g / mol, and most preferably ≥1100 g / mol.

[0112] In a premixed co-host in vapor-deposited OLEDs, the two host materials are required to have similar chemical or physical properties, such as molecular weight and sublimation temperature. The present invention has discovered that in solution-processed OLEDs, two host materials with different properties may enhance film-forming performance, thereby improving device performance. In addition to molecular weight and sublimation temperature, these properties may also include other properties, such as glass transition temperature and molecular volume. Therefore, for printed OLEDs, preferred embodiments of the organic mixture according to the present invention include:

[0113] The difference in molecular weight between the first compound H1 and the second compound H2 is ≥120 g / mol, preferably ≥140 g / mol, more preferably ≥160 g / mol, most preferably ≥180 g / mol.

[0114] The difference in sublimation temperature between the first compound H1 and the second compound H2 is ≥60K, preferably ≥70K, more preferably ≥75K, most preferably ≥80K.

[0115] The difference in glass transition temperature between the first compound H1 and the second compound H2 is ≥20K, preferably ≥30K, more preferably ≥40K, most preferably ≥45K.

[0116] The difference in molecular volume between the first compound H1 and the second compound H2 is ≥20%, preferably ≥30%, more preferably ≥40%, and most preferably ≥45%.

[0117] In other embodiments, at least one, and preferably both, of the first compound H1 and the second compound H2 in the organic mixture of the present invention has a solubility in toluene of ≥2 mg / mL, preferably ≥3 mg / mL, more preferably ≥4 mg / mL, and most preferably ≥5 mg / mL at 25°C.

[0118] As defined herein, the term "small molecule" refers to a molecule that is not a polymer, oligomer, dendrimer, or blend. In particular, a small molecule lacks a repeating structure. A small molecule has a molecular weight of ≤3000 g / mol, preferably ≤2000 g / mol, and most preferably ≤1500 g / mol.

[0119] Polymers include homopolymers, copolymers, and block copolymers. In the present invention, polymers also include dendrimers. For information on 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.].

[0120] Conjugated polymer is a polymer whose main chain backbone is mainly composed of sp 2 Hybrid orbitals are formed. Famous examples include polyacetylene and poly(phenylene vinylene). The C atoms on the main chain can also be replaced by other non-C atoms, and when the sp 2 When hybridization is interrupted by some natural defects, it is still considered a conjugated polymer. In addition, the conjugated polymers in the present invention also include those containing aryl amines, aryl phosphine, other heteroaromatics, organometallic complexes, etc. in the main chain.

[0121] In a particularly preferred embodiment, the organic mixture further comprises another organic functional material. The another organic functional material comprises a hole (also known as an electron hole) injection or transport material (HIM / HTM), a hole blocking material (HBM), an electron injection or transport material (EIM / ETM), an electron blocking material (EBM), an organic host material (Host), a singlet light emitter (fluorescent light emitter), a triplet light emitter (phosphorescent light emitter), an organic thermally excited delayed fluorescence material (TADF material), and in particular a luminescent organometallic complex. 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 or a polymer material.

[0122] In certain preferred embodiments, the organic mixture further comprises a light-emitting body, and the light-emitting body is selected from phosphorescent light-emitting bodies or TADF materials.

[0123] In a preferred embodiment, the organic mixture further comprises a phosphorescent light emitting body, wherein the weight percentage of the phosphorescent light emitting body is ≤20 wt%, preferably ≤15 wt%, and more preferably ≤10 wt%.

[0124] Phosphorescent emitters are also called triplet emitters. In a preferred embodiment, the phosphorescent emitter has the general formula M(L): n0 wherein M is a metal atom, L can be the same or different at each occurrence, is an organic ligand, which is bonded or coordinated to the metal atom M through one or more positions, and n0 is an integer greater than 1, preferably 1, 2, 3, 4, 5 or 6. Alternatively, these metal complexes are linked to a polymer through one or more positions, preferably through the organic ligand.

[0125] In a preferred embodiment, the metal atom M is selected from transition metal elements, lanthanides or actinides, preferably from Ir, Pt, Pd, Au, Rh, Ru, Os, Sm, Eu, Gd, Tb, Dy, Re, Cu or Ag, particularly preferably from Os, Ir, Ru, Rh, Re, Pd or Pt, most preferably from Ir or Pt.

[0126] Typically, phosphorescent emitters contain chelating ligands, i.e., ligands that coordinate to the metal via at least two binding points. Particularly preferred are triplet emitters containing two or three identical or different bidentate or polydentate ligands. Chelating ligands contribute to increasing the stability of the metal complex.

[0127] 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, with fluorine-containing or trifluoromethyl groups. The auxiliary ligand may preferably be selected from acetic acid, acetone, or picric acid.

[0128] In a preferred embodiment, the metal complex useful as triplet emitter has the following form:

[0129] The metal atom M is selected from transition metal elements, lanthanides or actinides, preferably Ir, Pt, Pd, Au, Rh, Ru, Os, Re, Cu, Ag, Ni, Co, W or Eu, and particularly preferably Ir, Au, Pt, W or Os.

[0130] Ar4 and Ar5 may be the same or different at each occurrence and are cyclic groups, wherein Ar4 contains at least one donor atom (i.e., an atom with a lone pair of electrons, such as nitrogen), through which the cyclic group coordinates to the metal; wherein Ar5 contains at least one carbon atom, through which the cyclic group is bonded to the metal; Ar4 and Ar5 are covalently bonded together and may each carry one or more substituents, which may be further bonded together by substituents; L' may be the same or different at each occurrence and is a bidentate chelating ancillary 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. Examples of organic ligands may be selected from phenylpyridine derivatives or 7,8-benzoquinoline derivatives. All of these organic ligands may be substituted, for example, with alkyl chains or fluorine- or silicon-containing substitutions. The ancillary ligand may preferably be selected from acetone acetate or picric acid.

[0131] In a particularly preferred embodiment, the phosphorescent emitter is a transition metal complex (preferably a metal complex of Ir or Pt) comprising at least one ligand or part of a ligand selected from the group consisting of:

[0132] Wherein T is selected from B, Al, Ga or In; K 1’ Is a direct bond selected from NR e PR e , O, S or Se; Y 1 -Y 15 are selected from C or N; Y' is selected from BR e NR e PR e ,O,S,Se,C=O,C=S,C=Se,C=NR e 、C=CRe R f 、S=O、SO2、CR e R f 、P(O)R e 、SiR e R f or GeR e R f ; R e and R f Can be fused or linked to form a ring; R a , R b , R c and R d are represented as a single to the maximum possible number of substituents or unsubstituted, respectively;

[0133] R a1 、R b1 、R c1 、R d1 、R a 、R b 、R c 、R d 、R e and R f are independently selected from H, D, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boron, arylalkyl, alkoxy, aryl, alkenyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfonamide, sulfoxide, phosphorus, selenoyl, or a combination of these groups; and R a1 、R b1 、R c1 、R d1 、R a 、R b 、R c 、R d Any two adjacent substituents may be fused or linked to form a ring or to form a multidentate ligand.

[0134] Examples of some phosphorescent materials and their applications can be found in the following patent documents and literature: WO200070655, WO200141512, WO200202714, WO200215645, EP1191613, EP1191612, EP1191614, WO2005033244, WO2005019373, US20050258742, WO200914 6770, WO2010015307, WO2010031485, WO2010054731, WO2010054728, WO2010086089, WO2010099 852, WO2010102709, US20070087219A1, US20090061681A1, US20010053462A1, Baldo, Thompson et 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,US20070252517A1,Johnson et al.,JACS105,1983,1795,Wrighton,JACS 96,1974,998,Ma et al.,Synth.Metals The entire contents of the above-listed patent documents and literature are hereby incorporated by reference into this document.

[0135] Some examples of suitable metal complexes as phosphorescent emitters are listed below, but are not limited to:

[0136] In another preferred embodiment, the organic mixture further comprises a fluorescent light emitting body, wherein the weight percentage of the fluorescent light emitting body is ≤15 wt%, preferably ≤10 wt%, and more preferably ≤8 wt%.

[0137] In another preferred embodiment, the organic mixture further comprises a TADF luminescent material, wherein the weight percentage of the TADF luminescent material is ≤15 wt%, preferably ≤10 wt%, and more preferably ≤8 wt%.

[0138] The following is a more detailed description of fluorescent luminescent materials (singlet luminophores) and TADF luminescent materials (but not limited to these).

[0139] 1. Singlet Emitter

[0140] Singlet emitters often have longer conjugated π-electron systems. To date, there have been many examples, such as styrylamine and its derivatives disclosed in JP2913116B and WO2001021729A1, and indenofluorene and its derivatives disclosed in WO2008 / 006449 and WO2007 / 140847.

[0141] In a preferred embodiment, the singlet emitter can be selected from monostyrylamine, distyrylamine, tertiary styrylamine, tetrastyrylamine, styrylphosphine, styryl ether and aromatic amine.

[0142] A monostyrylamine is a compound comprising an unsubstituted or substituted styryl group and at least one amine, preferably an aromatic amine. A distyrylamine is a compound comprising two unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine. A tert-styrylamine is a compound comprising three unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine. A tetrastyrylamine is a compound comprising four unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine. A preferred styrene is diphenylethylene, which may be further substituted. The corresponding phosphines and ethers are defined similarly to the amines. An arylamine or aromatic amine is a compound comprising three unsubstituted or substituted aromatic or heterocyclic rings directly attached to nitrogen. At least one of these aromatic or heterocyclic ring systems is preferably a fused ring system and preferably has at least 14 aromatic ring atoms. Preferred examples include aromatic anthracenamines, aromatic anthracenediamines, aromatic pyreneamines, aromatic pyrenediamines, aromatic chryseneamines, and aromatic chrysenediamines. An aromatic anthracenamine is a compound in which one diarylamine group is directly attached to anthracene, preferably at the 9 position. An aromatic anthracenediamine is a compound in which two diarylamine groups are directly attached to anthracene, preferably at the 9 and 10 positions. Aromatic pyreneamines, aromatic pyrenediamines, aromatic chrysamines, and aromatic chrysenediamines are similarly defined, with the diarylamine groups preferably attached to the 1 or 1,6 positions of the pyrene group.

[0143] Examples of singlet emitters based on vinylamine and aromatic amine, which are also preferred examples, can be found in the following patent documents: WO2006 / 000388, WO2006 / 058737, WO2006 / 000389, WO2007 / 065549, WO2007 / 115610, US7250532B2, DE102005058557A1, CN1583691A, JP08053397A, US6251531B1, US2006 / 210830A, EP1957606A1 and US2008 / 0113101A1. The entire contents of the above-listed patent documents are hereby incorporated herein by reference.

[0144] Examples of singlet emitters based on stilbene and its derivatives are disclosed in US Pat. No. 5,121,029.

[0145] Further preferred singlet emitters can be selected from indenofluorene-amines and indenofluorene-diamines, as disclosed in WO 2006 / 122630, benzindenofluorene-amines and benzindenofluorene-diamines, as disclosed in WO 2008 / 006449, and dibenzoindenofluorene-amines and dibenzoindenofluorene-diamines, as disclosed in WO 2007 / 140847.

[0146] Other materials that can be used as singlet emitters are polycyclic aromatic hydrocarbon compounds, especially derivatives of the following compounds: anthracene such as 9,10-di(2-naphthyl)anthracene, naphthalene, tetracene, xanthene, phenanthrene, pyrene (such as 2,5,8,11-tetra-t-butylperylene), indenopyrene, benzo-fused ring such as (4,4'-bis(9-ethyl-3-carbazolylvinyl)-1,1'-biphenyl), diindenopyrene, decacycloene, hexabenzophenone, fluorene, spirobifluorene, arylpyrene (such as US20060222886), arylenevinyl (such as US5121 029, US5130603), cyclopentadiene such as tetraphenylcyclopentadiene, rubrene, coumarin, rhodamine, quinacridone, pyran such as 4-(dicyanomethylene)-6-(4-(p-dimethylaminophenyl)-2-methyl)-4H-pyran (DCM), thiopyran, bis(azinyl)imine boron compounds (US2007 / 0092753A1), bis(azinyl)methylene compounds, carbostyryl compounds, oxazinones, benzoxazoles, benzothiazoles, benzimidazoles, and dione pyrrolopyrroles. Some materials for singlet emitters can be found in the following patent documents: US20070252517A1, US4769292, and US6020078. The entire contents of the above-listed patent documents are hereby incorporated herein by reference.

[0147] Some examples of suitable singlet emitters are listed below:

[0148] 2. Thermally activated delayed fluorescence materials (TADF materials)

[0149] Traditional organic fluorescent materials can only utilize 25% of the singlet excitons formed by electrical excitation for luminescence, resulting in a low internal quantum efficiency (up to 25%). Although phosphorescent materials, due to the strong spin-orbit coupling at the heavy atom center, enhance intersystem crossing, they can effectively utilize singlet and triplet excitons formed by electrical excitation for luminescence, achieving a device internal quantum efficiency of 100%. However, the high cost, poor material stability, and severe device efficiency roll-off of phosphorescent materials limit their application in OLEDs. Thermally activated delayed fluorescence (TADF) materials are the third generation of organic light-emitting materials developed after organic fluorescent and organic phosphorescent materials. These materials generally have a small singlet-triplet energy level difference (ΔEst), allowing triplet excitons to be converted to singlet excitons through anti-TAF crossing. This fully utilizes the singlet and triplet excitons formed by electrical excitation, resulting in a device internal quantum efficiency of 100%. Furthermore, the materials offer controllable structure, stable properties, low cost, and the absence of precious metals, making them promising for application in OLEDs.

[0150] TADF materials need to have a small singlet-triplet energy level difference, preferably ΔEst < 0.3 eV, second preferably ΔEst < 0.25 eV, more preferably ΔEst < 0.20 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.

[0151] Some examples of suitable TADF emitters are listed below:

[0152] In certain embodiments, the organic mixture according to the present invention has a solubility in toluene of ≥10 mg / mL at 25° C., preferably ≥15 mg / mL, and most preferably ≥20 mg / mL.

[0153] The present invention further relates to a composition or ink comprising an organic mixture as described above and at least one organic solvent.

[0154] When used in printing processes, ink viscosity and surface tension are important parameters. The appropriate surface tension parameters of the ink are suitable for a specific substrate and a specific printing method.

[0155] 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.

[0156] In another preferred embodiment, the viscosity of the ink according to the present invention at operating temperature or 25° C. is in the range of about 1 cps to 100 cps; more preferably, in the range of 1 cps to 50 cps; more preferably, in the range of 1.5 cps to 20 cps; and most preferably, in the range of 4.0 cps to 20 cps. Such a formulated composition will facilitate inkjet printing.

[0157] Viscosity can be adjusted by various methods, such as by selecting the appropriate solvent and the concentration of the functional material in the ink. The ink containing the organic mixture according to the present invention facilitates adjustment of the printing ink within an appropriate range according to the printing method used. Generally, the weight ratio of the functional material contained in the composition of the present invention is in the range of 0.3 wt% to 30 wt%, preferably in the range of 0.5 wt% to 20 wt%, more preferably in the range of 0.5 wt% to 15 wt%, even more preferably in the range of 0.5 wt% to 10 wt%, and most preferably in the range of 1 wt% to 5 wt%.

[0158] 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.

[0159] 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, dipentylbenzene, tripentylbenzene, pentyltoluene, o-xylene, m-xylene, p-xylene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1,2,3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, butylbenzene, dodecylbenzene, dihexylbenzene, dibutylbenzene, 1-methoxynaphthalene, cyclohexylbenzene, dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, 1-methylnaphthalene, 1,2,4-trichlorobenzene, 1,3-dipropoxybenzene, 4 ,4-difluorodiphenylmethane, 1,2-dimethoxy-4-(1-propenyl)benzene, diphenylmethane, 2-phenylpyridine, 3-phenylpyridine, N-methyldiphenylamine, 4-isopropylbiphenyl, α,α-dichlorodiphenylmethane, 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-dimethoxybenzene , 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.

[0160] 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.

[0161] 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.

[0162] In a preferred embodiment, the composition according to the present invention is a solution.

[0163] In another preferred embodiment, the composition according to the present invention is a suspension.

[0164] The composition in the embodiment of the present invention may include 0.01wt% to 20wt% of the organic 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 mixture.

[0165] 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.

[0166] Among them, suitable printing or coating techniques include (but are not limited to) gravure printing, inkjet printing, nozzle printing, letterpress printing, screen printing, dip coating, spin coating, blade coating, roller printing, twist roller printing, lithographic printing, flexographic printing, rotary printing, spraying, brushing or pad printing, slot extrusion coating, etc. Preferred are gravure printing, nozzle printing and inkjet printing. The solution or suspension may further include one or more components such as surfactants, lubricants, wetting agents, dispersants, hydrophobic agents, adhesives, etc., for adjusting viscosity, film-forming properties, improving adhesion, etc. For detailed information on printing techniques and their requirements for relevant solutions, such as solvents, concentrations, and viscosities, please refer to "Handbook of Print Media: Technologies and Production Methods" edited by Helmut Kipphan, ISBN 3-540-67326-1.

[0167] The present invention further relates to an organic compound having a structure represented by chemical formula (II-1): wherein the linking group L does not contain a cyano group, and L is selected from the following electron-withdrawing groups, which may be further substituted with any other group:

[0168] where X 1 -X 8 Selected from CR or N, and at least one of them is N; Z1, Z2, and Z3 independently represent N(R), C(R)2, Si(R)2, O, C=N(R), C=C(R)2, P(R), P(=O)R, S, S=O, SO2 or none, but at least one of them is not none; wherein R can be selected from the following groups: hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl; the definitions of other symbols are the same as those of chemical formula (II-1).

[0169] In a preferred embodiment, the structure is represented by chemical formula (II-1), wherein: 1) n5 ≥ 1, and at least one R5 comprises an electron-withdrawing group; 2) n6 ≥ 1, and at least one R6 comprises an electron-withdrawing group. Suitable and preferred electron-withdrawing groups are as described above. More preferably, at least one of R5 and H6 comprises a weak electron-withdrawing group as described above.

[0170] where X 1 -X 8Selected from CR or N, and at least one of them is N; Z1, Z2, and Z3 independently represent N(R), C(R)2, Si(R)2, O, C=N(R), C=C(R)2, P(R), P(=O)R, S, S=O, SO2 or none, but at least one of them is not none; wherein R can be selected from the following groups: hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl.

[0171] In some preferred embodiments, the organic compound of the present invention is characterized by having any one of the chemical formulas (II-1a) to (II-1e):

[0172] In a preferred embodiment, the organic compound described above, wherein n5+n6≥1, and at least one R5 or R6 contains an electron-withdrawing group.

[0173] In some more preferred embodiments of the organic compound, L is selected from the following electron-withdrawing groups, which may be further substituted with any substitution:

[0174] wherein n is selected from an integer from 1 to 3; X 1 -X 8 Selected from CR or N, and at least one of them is N; Z1, Z2, and Z3 independently represent N(R), C(R)2, Si(R)2, O, C=N(R), C=C(R)2, P(R), P(=O)R, S, S=O, SO2 or none, but at least one of them is not none; wherein R can be selected from the following groups: hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl.

[0175] Preferred organic compounds according to the chemical formula (II-1), chemical formula (II-1a)-(II-1e) and chemical formula (II-1a-1)-(II-1e-1) are shown below, but are not limited to:

[0176] In a more preferred embodiment, the organic compound according to the present invention is at least partially deuterated, preferably ≥10% of the H is deuterated, more preferably ≥20% of the H is deuterated, most preferably ≥30% of the H is deuterated, and most preferably ≥40% of the H is deuterated.

[0177] Based on the above-mentioned organic mixture and organic compound, the present invention further provides an application of the above-mentioned organic mixture and organic compound, i.e., applying the organic mixture or organic compound to an organic electronic device. The organic electronic device may 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 (OLED), an organic laser, an organic spintronic device, an organic sensor, and an organic plasmon emitting diode (OPED), in particular an OLED. In an embodiment of the present invention, the organic mixture or organic compound is preferably used in the light-emitting layer of an OLED device.

[0178] The present invention further provides a photovoltaic device comprising at least one organic mixture or organic compound as described above.

[0179] In some preferred embodiments, the optoelectronic device is 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 sensor or an organic plasmon emitting diode (Organic Plasmon Emitting Diode).

[0180] In some more preferred embodiments, the optoelectronic device is an organic electroluminescent device, comprising a substrate, an anode, at least one light-emitting layer, a cathode, and optionally a hole transport layer or an electron transport layer. In certain embodiments, the hole transport layer comprises an organic mixture or organic compound according to the present invention. In a preferred embodiment, the light-emitting layer comprises an organic mixture or organic compound according to the present invention. More preferably, the light-emitting layer comprises an organic mixture or organic compound according to the present invention and at least one light-emitting material, wherein the light-emitting material may be a fluorescent emitter, a phosphorescent emitter, or a TADF material.

[0181] The device structure of the organic electroluminescent device is described below, but is not limited thereto.

[0182] 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 if 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 with a glass transition temperature (Tg) of above 150°C, preferably above 200°C, more preferably above 250°C, and most preferably above 300°C. Examples of suitable flexible substrates are polyethylene terephthalate (PET) and polyethylene (2,6-naphthalene) (PEN).

[0183] The anode may comprise a conductive metal or metal oxide, or a conductive polymer. The anode can readily inject holes into the hole injection layer (HIL), hole transport layer (HTL), or light-emitting layer. In one embodiment, the absolute value of the difference between the work function of the anode and the HOMO energy level or valence band energy level of the light-emitting material in the light-emitting layer or the p-type semiconductor material serving as the HIL, HTL, or 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), and the like. Other suitable anode materials are known and can be readily selected for use by one of ordinary skill 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), and the like. In certain embodiments, the anode is patterned. Patterned ITO conductive substrates are commercially available and can be used to prepare devices according to the present invention.

[0184] The cathode may comprise a conductive metal or metal oxide. The cathode can readily inject electrons into the EIL or ETL or directly into the light-emitting layer. In one embodiment, the absolute 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 serving as the electron injection layer (EIL), electron transport layer (ETL), or 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 in OLEDs are possible cathode materials for the devices of the present invention. Examples of cathode materials include, but are not limited to, Al, Au, Ag, Ca, Ba, Mg, LiF / Al, MgAg alloys, BaF2 / Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO, and the like. 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), and the like.

[0185] 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 and in WO2010135519A1, US20090134784A1, and WO2011110277A1, the entire contents of which are hereby incorporated by reference.

[0186] In a preferred embodiment, in the organic electroluminescent device according to the present invention, the light-emitting layer thereof comprises the organic mixture or organic compound of the present invention.

[0187] In another preferred embodiment, the light-emitting layer of the organic electroluminescent device can be formed by one of the following two methods: (1) the first compound H1 and the second compound H2 containing a co-host are deposited as one source; (2) the first compound H1 and the second compound H2 are evaporated as two separate sources.

[0188] In another preferred embodiment, in the organic electroluminescent device according to the present invention, the electron transport layer thereof comprises the organic mixture or organic compound according to the present invention.

[0189] According to the organic electroluminescent device of the present invention, the emission wavelength is between 300 nm and 1000 nm, preferably between 350 nm and 900 nm, and more preferably between 400 nm and 800 nm.

[0190] The present invention also relates to applications of the organic 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.

[0191] Example

[0192] 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 appended claims summarize the scope of the present invention. Under the guidance of the concept of the present invention, those skilled in the art should realize 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.

[0193] 1. Synthesis of compounds

[0194] Synthesis of intermediate 1b:

[0195] Intermediate 1a was prepared from 2,4-dichloropyridine in the presence of [Ir(μ-OMe)COD]2 (reference: DOI: 10.1039 / C4OB01565G). Intermediate 1a (100 g), tetrakistriphenylphosphine palladium (1 g), iodobenzene (110 g), and potassium carbonate (67 g) were dissolved in a mixture of toluene (1000 mL), ethanol (200 mL), and water (200 mL). The mixture was heated to 100°C and stirred for 12 hours. After cooling to room temperature, the reaction solution was extracted with a large amount of deionized water and dichloromethane, and the organic phase was retained. The organic solvent was removed by vacuum distillation, and the product was purified by silica gel column chromatography to obtain 90 g of intermediate 1b in a 90% yield. Product characterization: MS (ASAP) = 224.

[0196] Synthesis of compound 1:

[0197] Under nitrogen, a three-necked flask was charged with 2-bromoindolo[3,2,1-JK]carbazole (30g) and dry THF (300mL). The atmosphere was replaced with nitrogen three times and then cooled to -78°C in an acetone bath. 15mL of n-butyllithium solution (n-BuLi, 2.5mol / L in n-hexane) was added. The reaction was allowed to proceed at low temperature for 45 minutes, followed by the slow dropwise addition of 30mL of trimethyl borate. The reaction was maintained at -78°C for another 45 minutes, then allowed to naturally return to room temperature and stirred for 6 hours before stopping the reaction. The reaction was quenched with saturated ammonium chloride aqueous solution, extracted with ethyl acetate and deionized water, and the organic phase was washed twice, recrystallized with petroleum ether, dried, and filtered to yield 25g of crude product 1c. The product was then carried on to the next step without further treatment.

[0198] Under nitrogen, a three-necked flask was charged with 1c (100 g), intermediate 1b (120 g), potassium carbonate (25 g), tetrakistriphenylphosphine palladium (2 g), and 3000 mL of toluene / 500 mL of ethanol / 500 mL of water. The atmosphere was replaced with nitrogen three times, the temperature was raised to 100°C, and the reaction was terminated by heating under reflux for 12 h. The temperature was then lowered. The product was extracted with ethyl acetate and deionized water, and the organic phase was washed twice with water, dried, filtered, and the filtrate was spin-dried to obtain 110 g of crude product. Column chromatography (petroleum ether / ethyl acetate = 15:1) yielded 96 g of compound 1, with a yield of 96%. Mass spectrometry analysis determined the molecular ion mass (MS(ASAP)) = 633 (calculated value: 633.75).

[0199] Synthesis of compound 2:

[0200] Under nitrogen, a three-necked flask was charged with 1c (100g), 2a (120g), potassium carbonate (25g), tetrakistriphenylphosphine palladium (2g), and 3000mL toluene / 500mL ethanol / 500mL water. The atmosphere was replaced with nitrogen three times, the temperature was raised to 100°C, and the reaction was terminated by heating under reflux for 12 hours. The temperature was then lowered. The mixture was extracted with ethyl acetate and deionized water, and the organic phase was washed twice with water, dried, filtered, and the filtrate was spin-dried to obtain 120g of the crude product. Column chromatography (petroleum ether / ethyl acetate = 15:1) was performed to collect the product, compound 2, to yield 99g, with a yield of 99%. The molecular ion mass (MS(ASAP)) determined by mass spectrometry was 635 (calculated value: 635.73).

[0201] Synthesis of compound 3:

[0202] Under nitrogen, a three-necked flask was charged with 1c (100g), 3a (120g), potassium carbonate (25g), tetrakistriphenylphosphine palladium (2g), and 3000mL toluene / 500mL ethanol / 500mL water. The atmosphere was replaced with nitrogen three times, the temperature was raised to 100°C, the reaction was stopped by heating under reflux for 12h, and the temperature was cooled. The organic phase was extracted with ethyl acetate and deionized water, washed twice with water, dried, filtered, and the filtrate was spin-dried to obtain 120g of crude product. Column chromatography (petroleum ether / ethyl acetate = 15:1) collected the product, compound 3, to yield 80g, with an 80% yield. Mass spectrometry analysis determined the molecular ion mass MS (ASAP) = 725 (calculated value: 724.83).

[0203] Synthesis of compound 4:

[0204] Under nitrogen, a three-necked flask was charged with 1c (100g), 4a (120g), potassium carbonate (25g), tetrakistriphenylphosphine palladium (2g), and 3000mL toluene / 500mL ethanol / 500mL water. The atmosphere was replaced with nitrogen three times, the temperature was raised to 100°C, and the reaction was terminated by heating under reflux for 12 hours. The temperature was then lowered. The mixture was extracted with ethyl acetate and deionized water, and the organic phase was washed twice with water, dried, filtered, and the filtrate was spin-dried to obtain 90g of the crude product. Column chromatography (petroleum ether / ethyl acetate = 15:1) yielded 89g of compound 4, a 90% yield. Mass spectrometry analysis determined the molecular ion mass (MS(ASAP)) = 634 (calculated: 634.74).

[0205] Synthesis of compound 5:

[0206] Under nitrogen, a three-necked flask was charged with 5a (100 g), NIS (100 g), and 1000 mL of dichloromethane. The atmosphere was replaced with nitrogen three times, and the reaction was stopped by placing it in an ice-water bath for 36 hours, allowing it to return to room temperature. The mixture was extracted with ethyl acetate and deionized water, and the organic phase was washed twice, dried, filtered, and the filtrate was evaporated to dryness to obtain 120 g of the crude product. Column chromatography (petroleum ether / ethyl acetate = 15:1) was used to collect 90 g of the product 5b, yielding 90% (90%).

[0207] Under nitrogen, a three-necked flask was charged with 5b (100 g), phenylboronic acid (150 g), potassium carbonate (25 g), tetrakistriphenylphosphine palladium (2 g), and 3000 mL of toluene / 500 mL of ethanol / 500 mL of water. The atmosphere was replaced with nitrogen three times, the temperature was raised to 100°C, and the reaction was stopped by heating under reflux for 12 h. The temperature was then lowered. The product was extracted with ethyl acetate and deionized water, and the organic phase was washed twice with water, dried, filtered, and the filtrate was evaporated to dryness to obtain 100 g of the crude product. The product 5c was collected by column chromatography (petroleum ether / ethyl acetate = 15:1) to obtain 90 g of the product, with a yield of 90%.

[0208] Under nitrogen, a three-necked flask was charged with 5c (30 g) and dry THF (300 mL). The mixture was replaced with nitrogen three times and then cooled to -78°C in an acetone bath. 15 mL of n-butyllithium solution (n-BuLi, 2.5 mol / L in n-hexane) was added. The reaction was allowed to react at low temperature for 45 minutes, followed by the slow dropwise addition of 30 mL of trimethyl borate. The reaction was maintained at -78°C for another 45 minutes, then allowed to naturally return to room temperature and stirred for 6 hours before stopping the reaction. The mixture was quenched with saturated aqueous ammonium chloride and extracted with ethyl acetate and deionized water. The organic phase was washed twice, recrystallized with petroleum ether, dried, and filtered to obtain 20 g of crude product 5d. The product was directly carried to the next step without further treatment.

[0209] Under nitrogen, a three-necked flask was charged with 5d (100g), 4a (120g), potassium carbonate (25g), tetrakistriphenylphosphine palladium (2g), and 3000mL toluene / 500mL ethanol / 500mL water. The atmosphere was replaced with nitrogen three times, the temperature was raised to 100°C, the reaction was stopped by heating under reflux for 12 hours, and the temperature was cooled. The organic phase was extracted with ethyl acetate and deionized water, washed twice with water, dried, filtered, and the filtrate was spin-dried to obtain 60g of crude product. Column chromatography (petroleum ether / ethyl acetate = 15:1) collected the product, compound 5, to yield 60g, with a yield of 60%. Mass spectrometry analysis determined the molecular ion mass (MS(ASAP)) = 940 (calculated value: 939.19).

[0210] Synthesis of compound 6:

[0211] The synthesis method of intermediate 6c is similar to that of intermediate 5d, except that 2-pyridineboronic acid is used instead of phenylboronic acid.

[0212] Under nitrogen, a three-necked flask was charged with 6c (100g), 4a (120g), potassium carbonate (25g), tetrakistriphenylphosphine palladium (2g), and 3000mL toluene / 500mL ethanol / 500mL water. The atmosphere was replaced with nitrogen three times, the temperature was raised to 100°C, the reaction was stopped by heating under reflux for 12 hours, and the temperature was cooled. The organic phase was extracted with ethyl acetate and deionized water, washed twice with water, dried, filtered, and the filtrate was spin-dried to obtain 78g of crude product. Column chromatography (petroleum ether / ethyl acetate = 15:1) collected the product, compound 6, to yield 78g, with an 80% yield. Mass spectrometry analysis determined the molecular ion mass MS (ASAP) = 943 (calculated value: 943.09).

[0213] Synthesis of compound 7:

[0214] Under nitrogen, a three-necked flask was charged with 5a (100 g), phenylboric acid (150 g), potassium carbonate (25 g), tetrakistriphenylphosphine palladium (2 g), and 3000 mL of toluene / 500 mL of ethanol / 500 mL of water. The atmosphere was replaced with nitrogen three times, the temperature was raised to 100°C, and the reaction was terminated by heating under reflux for 12 hours. The temperature was then lowered. The reaction was extracted with ethyl acetate and deionized water, and the organic phase was washed twice with water, dried, filtered, and the filtrate was evaporated to dryness to obtain 100 g of crude product 7a. The product 7a was collected by column chromatography (petroleum ether / ethyl acetate = 15:1) to yield 95 g, a 95% yield.

[0215] Under nitrogen, 7a (100 g), NBS (30 g), and 1000 mL of dichloromethane were added to a three-necked flask. The atmosphere was replaced with nitrogen three times, and the reaction was stopped in an ice-water bath for 36 hours, after which the mixture was allowed to return to room temperature. The reaction was extracted with ethyl acetate and deionized water. The organic phase was washed twice, dried, filtered, and the filtrate was spin-dried to afford 100 g of crude product 7b. Column chromatography (petroleum ether / ethyl acetate = 15:1) yielded 45 g of product 7b, a 45% yield.

[0216] Under nitrogen, a three-necked flask was charged with 7b (30 g) and dry THF (300 mL). The atmosphere was replaced with nitrogen three times, then cooled to -78°C in an acetone bath. 15 mL of n-butyllithium solution (n-BuLi, 2.5 mol / L in n-hexane) was added. The reaction was allowed to react at low temperature for 45 minutes, followed by the slow dropwise addition of 30 mL of trimethyl borate. The reaction was maintained at -78°C for another 45 minutes, then naturally returned to room temperature and stirred for 6 hours before stopping the reaction. The reaction was quenched with saturated aqueous ammonium chloride, extracted with ethyl acetate and deionized water, and the organic phase was washed twice, recrystallized with petroleum ether, dried, and filtered to yield 25 g of crude product 7c. The product was then carried on to the next step without further treatment.

[0217] Under nitrogen, a three-necked flask was charged with 7c (100g), 4a (120g), potassium carbonate (25g), tetrakistriphenylphosphine palladium (2g), and 3000mL toluene / 500mL ethanol / 500mL water. The atmosphere was replaced with nitrogen three times, the temperature was raised to 100°C, and the reaction was terminated by heating under reflux for 12 hours. The temperature was then lowered. The mixture was extracted with ethyl acetate and deionized water, and the organic phase was washed twice, dried, filtered, and the filtrate was spin-dried to give 90g of crude compound 7. Column chromatography (petroleum ether / ethyl acetate = 15:1) yielded 60g of compound 7, with a yield of 60%. Mass spectrometry analysis determined the molecular ion mass (MS(ASAP)) = 787 (calculated: 786.94).

[0218] Synthesis of compound 8:

[0219] Under nitrogen protection, add 1c (50g), 4a (120g), potassium carbonate (25g), tetrakistriphenylphosphine palladium (2g) and 3000mL toluene / 500mL ethanol / 500mL water to a three-necked flask, replace with nitrogen three times, heat to 100℃ for reaction, heat under reflux for 12 hours 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 60g of crude product 8a. Separate by column chromatography (petroleum ether / ethyl acetate = 15:1), collect 50g of product 8a, with a yield of 45%.

[0220] Under nitrogen, a three-necked flask was charged with 8a (100g), 7b (100g), potassium carbonate (25g), tetrakistriphenylphosphine palladium (2g), and 3000mL toluene / 500mL ethanol / 500mL water. The atmosphere was replaced with nitrogen three times, the temperature was raised to 100°C, and the reaction was terminated by heating under reflux for 12 hours. The temperature was then cooled. The product was extracted with ethyl acetate and deionized water, and the organic phase was washed twice with water, dried, filtered, and the filtrate was spin-dried to obtain 80g of the crude product. The product, compound 8, was isolated by column chromatography (petroleum ether / ethyl acetate = 15:1) to yield 75g, a 75% yield. The molecular ion mass, MS (ASAP), determined by mass spectrometry, was 710 (calculated value: 710.84).

[0221] Synthesis of compound 9:

[0222] The synthesis of compound 9 was similar to that of compound 7, except that 2-pyridineboronic acid was used instead of phenylboronic acid in the first step to obtain compound 9 with a yield of 35%. The molecular ion mass determined by mass spectrometry was MS (ASAP) = 789 (calculated value: 788.91).

[0223] Synthesis of compound 10:

[0224] Under nitrogen protection, add 1c (50g), 10a (120g), potassium carbonate (25g), tetrakistriphenylphosphine palladium (2g) and 3000mL toluene / 500mL ethanol / 500mL water to 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 60g of crude product 10b. Separate by column chromatography (petroleum ether / ethyl acetate = 15:1), collect product 10b to obtain 50g, with a yield of 45%.

[0225] Under nitrogen, a three-necked flask was charged with 10b (100g), 7b (100g), potassium carbonate (25g), tetrakistriphenylphosphine palladium (2g), and 3000mL toluene / 500mL ethanol / 500mL water. The atmosphere was replaced with nitrogen three times, the temperature was raised to 100°C, the reaction was stopped by heating under reflux for 12 hours, and the temperature was cooled. The organic phase was extracted with ethyl acetate and deionized water, washed twice with water, dried, filtered, and the filtrate was spin-dried to obtain 80g of crude compound 10. Column chromatography (petroleum ether / ethyl acetate = 15:1) collected the product, compound 10, to yield 35g, a 35% yield. Mass spectrometry analysis determined the molecular ion mass (MS(ASAP)) = 711 (calculated value: 711.83).

[0226] 2. Preparation of the Mixture

[0227] H1-1 and H1-2 as shown in the following table will be used as the first compound H1 in the mixture

[0228] The first compound H1 and the second compound H2 in Table 1 were mixed as evenly as possible according to a mass ratio of 1:1, and then the mixture was placed in a -3 In a 10-100-torr vacuum environment, the temperature is raised to completely melt the two host materials. Once mixed, the mixture is cooled to room temperature to solidify, and then ground into a powder using a ball mill for later use. The resulting mixture 1 and mixture 2 can be used as a blue or green phosphorescent host.

[0229] Table 1: Composition of the mixture

[0230] 3. Energy level structure of compounds

[0231] The energy levels of organic compounds can be calculated through quantum calculations, such as using TD-DFT (time-dependent density functional theory) with Gaussian 09W (Gaussian Inc.). For detailed simulation methods, see WO2011141110. The molecular geometry is first optimized using the semi-empirical method "Ground State / Semi-empirical / Default Spin / AM1" (Charge 0 / Spin Singlet). The energy structure of the organic molecule is then calculated using TD-DFT (time-dependent density functional theory) using the "TD-SCF / DFT / Default Spin / B3PW91" basis set "6-31G(d)" (Charge 0 / Spin Singlet). The HOMO and LUMO energy levels are calculated using the following calibration formulas, using S1 and T1 as is. HOMO(eV)=((HOMO(G)×27.212)-0.9899) / 1.1206 LUMO(eV)=((LUMO(G)×27.212)-2.0041) / 1.385

[0232] HOMO(G) and LUMO(G) are the direct calculation results of Gaussian 09W, and the unit is Hartree. The results are shown in Table 2:

[0233] Table 2

[0234] 4. Preparation and Characterization of OLED Devices

[0235] The following is a detailed description of the preparation process of the OLED device using the above-mentioned embodiments:

[0236] Device Example 1-Device Example 6:

[0237] The single-cell blue light device structure is HT-1:PD (97:3, 10nm) / HT-1 (50nm) / HT-2 (5nm) / BH:BD = 98:2 (20nm) / HB (5nm) / ET:LiQ = 50:50 (25nm) / Yb (1nm) / Ag (80nm), and is prepared according to the following steps:

[0238] a. Cleaning of ITO (Indium Tin Oxide) conductive glass substrates: Wet clean with Decon90 surfactant solution, then rinse three times with water and isopropyl alcohol, blow dry with nitrogen, and bake at 120°C for 20 minutes before treating the substrate with nitrogen plasma.

[0239] b. Evaporation: Move the ITO substrate into the vacuum vapor deposition equipment and place it in a high vacuum (1×10 -6 At 100 mbar, two evaporation sources were used to vaporize the materials at different rates, resulting in a 97:3 HT-1:PD ratio, forming a 10nm thick hole injection layer. Compound HT-1 was then evaporated on the HI layer to form a 50nm hole transport layer, followed by a 5nm light-emitting auxiliary layer (HT-2) on the hole transport layer. Two evaporation sources were then used to vaporize the materials at different rates, resulting in a 98:2 weight ratio of BH:BD, forming a 20nm light-emitting layer. A hole blocking layer (HB, 5nm) was then evaporated, followed by co-deposition of an electron transport material and LiQ in separate evaporation units at 50% by weight, forming an electron transport layer. A 1nm layer of Yb was then deposited as an electron injection layer, and finally an 80nm thick Ag cathode was deposited on the electron injection layer.

[0240] c. Packaging: The device is encapsulated with UV-curable resin in a nitrogen glove box.

[0241] The device performance of the above embodiment and comparative example was tested, as shown in Table 3. The driving voltage and current efficiency were measured at 10 mA / cm 2 The device life of T95 is tested at a constant current density of 20mA / cm 2 The time it takes for the brightness to decay to 95%.

[0242] Table 3

[0243] Compared with device comparison example 1, the current efficiency and life of device examples 1 to 6 are significantly improved, indicating that the organic compounds of the present invention are used as electron transport materials in OLED devices to improve the current efficiency and life of the devices, while also reducing the driving voltage of the devices.

[0244] Device Example 7-Device Example 12:

[0245] The stacked blue light device structure is HT-1:PD (97:3, 10nm) / HT-1 (50nm) / HT-2 (5nm) / BH:BD=98:2 (20nm) / HB (5nm) / ET-2:LiQ=50:50 (25nm) / N-CGL:Yb=98.5:1.5 (10nm) / HT-1:PD=95:5 (10nm) / HT-1 (50nm) / HT-2 (5nm) / BH:BD=98:2 (20nm) / HB (5nm) / ET-2:LiQ=50:50 (25nm) / Yb (1nm) / Ag (80nm), and is prepared according to the following steps:

[0246] a. Cleaning of ITO (Indium Tin Oxide) conductive glass substrate: The cleaning method is the same as that in the single-section device embodiment.

[0247] b. Evaporation: Move the ITO substrate into the vacuum vapor deposition equipment and place it in a high vacuum (1×10 -6 Using two evaporation sources at different rates, the materials were vaporized to a ratio of HT-1:PD of 97:3, forming a 10nm thick hole injection layer. Compound HT-1 was then deposited on the HI layer to form a 50nm thick hole transport layer, followed by a 5nm thick light-emitting auxiliary layer (HT-2) on top of the hole transport layer. Using two evaporation sources, the materials were then vaporized at different rates to a weight ratio of BH:BD of 98:2, forming a 20nm thick light-emitting layer. Then, a hole blocking layer (HB, 5nm) was evaporated, and then ET-2 and LiQ were placed in different evaporation units and co-deposited at a ratio of 50 weight percent to obtain a 25nm electron transport layer. Subsequently, two evaporation sources were used to control the vaporization of the N-type charge generation material and Yb at different rates, so that the weight ratio of N-type charge generation material: Yb was 98.5:1.5, forming an N-type charge generation layer (N-CGL) with a thickness of 10nm; then, two evaporation sources were used to vaporize the materials at different rates so that the ratio of HT-1:PD was 95:5, forming a P-type charge generation layer (P-CGL) with a thickness of 10nm; then, a hole transport layer, a light-emitting auxiliary layer, a light-emitting layer, a hole blocking layer and an electron transport layer were evaporated in sequence under the same conditions as above; then, 1nm of Yb was deposited as an electron injection layer, and finally, an Ag cathode with a thickness of 80nm was deposited on the electron injection layer.

[0248] c. Packaging: The same packaging method as in the single-cell device embodiment.

[0249] Table 4

[0250] As can be seen from Table 4, when other materials in the stacked OLED device are the same, using the organic compound of the present invention as the N-type charge generation layer, the device has a lower driving voltage and a higher external quantum efficiency.

[0251] Preparation and characterization of (blue light) device examples 13 to 21:

[0252] The following is a detailed description of the preparation process of the above-mentioned OLED device using 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 comparative example 3 are as follows:

[0253] a. Cleaning of ITO (Indium Tin Oxide) conductive glass substrates: Use various solvents (such as one or more of chloroform, acetone or isopropyl alcohol) to clean, and then perform ultraviolet ozone treatment.

[0254] b. HI (10 nm), HT-1 (60 nm), PH-1 (5 nm), host material: 10% BD (35 nm), ET-2 (5 nm), ET-1:Liq (50:50; 30 nm), Liq (2 nm), Al (100 nm) under 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 At 100 mbar, a resistive heating evaporation source was used to form a 10nm thick HI layer. A 60nm thick HT-1 and a 5nm thick PH-1 layer were then formed on the HI layer. Subsequently, an N-type host (EH-1) was placed in one evaporation unit, PH-1 in another, and compound BD as a dopant in another. The materials were vaporized at different rates to achieve a host:dopant weight ratio of 90:10 (for the case of using two hosts, the weight ratio of N-type host:PH-1:BD was 45:45:10). A 35nm thick luminescent layer was formed on the hole transport layer. A 5nm thick ET-2 layer was then deposited on the luminescent layer. ET-1 and Liq were then co-deposited in separate evaporation units at a 50 wt% ratio, forming a 30nm thick electron transport layer. A 2nm thick Liq was then deposited on the electron transport layer as an electron injection layer. Finally, a 100nm thick Al cathode was deposited on the electron injection layer.

[0255] c. Packaging: The device is encapsulated with UV-curable resin in a nitrogen glove box.

[0256] The device performance of the above embodiments and comparative examples was tested, as shown in Table 5. The device life LT95 refers to the time it takes for the brightness to decay to 95% at a constant current density, relative to the value of the comparative example.

[0257] The implementation method of device examples 13 to 21 is the same as that of device comparison example 3, except that different mixture combinations are used to replace the main material in the comparison example (wherein the co-host refers to two compounds placed in different evaporation units, 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.

[0258] Table 5

[0259] As can be seen from Table 5, when other materials in a blue OLED device are the same, using the mixture of the present invention as the main material will significantly improve the device life, although the efficiency of the device is not greatly improved.

[0260] Preparation and characterization of (blue light) device examples 22 to 30:

[0261] The following describes in detail the preparation process of the OLED device using the above-mentioned embodiments.

[0262] The structure of the green OLED device is: ITO / HI (30 nm) / HI-1 (50 nm) / HT-2 (10 nm) / EML (40 nm) / ET:Liq (30 nm) / Liq (1 nm) / Al (100 nm). The preparation steps of device Example 22 are as follows:

[0263] a. Cleaning of ITO (Indium Tin Oxide) conductive glass substrates: Use various solvents (such as one or more of chloroform, acetone or isopropyl alcohol) to clean, and then perform ultraviolet ozone treatment.

[0264] b. In high vacuum (1×10 -6 mbar) by thermal evaporation: the ITO substrate was moved into the vacuum vapor deposition equipment and heated in a high vacuum (1×10 -6At 100 mbar, a resistive heating evaporation source was used to form a 30nm thick HI layer. A 50nm thick HT-1 layer and a 10nm thick HT-2 layer were then formed on the HI layer. A 40nm thick luminescent layer (EL) was then formed on the hole transport layer, controlling the weight ratio of Compound 1:PH-G1:Dopant to 50:50:10. ET and LiQ were then co-deposited at 50 wt% each in separate evaporation units to form a 30nm thick electron transport layer (ETL) on the EL. A 1nm thick LiQ layer was then deposited on the ETL as an electron injection layer (EIL). Finally, a 100nm thick Al cathode was deposited on the EIL.

[0265] c. Packaging: The device is encapsulated with UV-curable resin in a nitrogen glove box.

[0266] The implementation methods of device examples 23 to 30 and comparative example 4 are the same as above, except that different co-hosts are used instead. The co-hosts refer to two compounds placed in different evaporation units, with the weight ratio of the materials controlled to be 50:50.

[0267] Table 6

[0268] The device performance of the above embodiment and comparative example was tested, as shown in Table 6. The driving voltage and current efficiency were measured at 10 mA / cm 2 The device life of T95 is tested at a constant current density of 20mA / cm 2 The time for the brightness to decay to 95%. According to the test, the performance of the mixture of the present invention as a green light host, especially the life span, is significantly improved.

[0269] The above-described embodiments merely illustrate several implementations of the present invention, and their descriptions are relatively specific and detailed. However, they should not be construed as limiting the scope of the patent. It should be noted that a person skilled in the art may make various modifications and improvements without departing from the scope of the present invention, and these modifications and improvements fall within the scope of protection of the present invention. Therefore, the scope of protection of the patent for this invention shall be based on the appended claims.

Claims

1. An organic mixture comprising a first compound H1 and a second compound H2, characterized in that: The first compound H1 is selected from chemical formula (I-1) or (I-2), and the second compound H2 is selected from chemical formula (II-1): Ar1-Ar3 are selected from substituted or unsubstituted aromatic or heteroaromatic groups having 5 to 40 ring atoms, or aryloxy or heteroaryloxy groups having 5 to 40 ring atoms, or combinations of these groups, wherein one or more of these groups can form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and / or with the ring to which they are bonded; L is a divalent bridging group selected from a substituted or unsubstituted aromatic group or heteroaromatic group having 5 to 20 ring atoms, and the bond connecting L to the two indole[3,21-jk]carbazoles is not a CN bond; R1-R6 are substituents which, at each occurrence, may be identical or different and are selected from D, or linear alkyl, alkoxy or thioalkoxy groups having 1 to 20 carbon atoms, or branched or cyclic alkyl, alkoxy, thioalkoxy or silyl groups having 3 to 20 carbon atoms, or keto groups having 1 to 20 carbon atoms, or alkoxycarbonyl groups having 2 to 20 carbon atoms, or aryloxycarbonyl groups having 7 to 20 carbon atoms, or cyano, carbamoyl, haloformyl, formyl, isocyanate, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, CF3, Cl, Br, F, 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; n1, n3, n4 are integers selected from 0 to 7; n2 is an integer selected from 0 to 8; n5 and n6 are selected from integers from 0 to 10.

2. The organic mixture according to claim 1, characterized in that: The first compound H1 and the second compound H2 form a type II heterojunction structure, and min(LUMO(H1)-HOMO(H2),LUMO(H2)-HOMO(H1))≤min(E T1 (H1),E T1 (H2))+0.1eV, where HOMO(H1), LUMO(H1) and E T1 (H1) are the highest occupied molecular orbital, lowest unoccupied molecular orbital, and triplet energy level of the first compound H1; HOMO(H2), LUMO(H2) and E T1 (H2) are the highest occupied molecular orbital, lowest unoccupied molecular orbital, and triplet energy level of H2 of the second compound, respectively.

3. The organic mixture according to claim 1 or 2, characterized in that The first compound H1 is selected from any one of chemical formulas (I-1a), (I-1b) or (I-2a):

4. The organic mixture according to any one of claims 1 to 3, characterized in that The second compound H2 is selected from any one of chemical formulas (II-1a) to (II-1e):

5. The organic mixture according to any one of claims 1 to 4, characterized in that The L is selected from the following electron-withdrawing groups, which may be further substituted with any substitution: wherein n is selected from an integer from 1 to 3; X 1 -X 8 Selected from CR or N, and at least one of them is N; Z1, Z2, and Z3 independently represent N(R), C(R)2, Si(R)2, O, C=N(R), C=C(R)2, P(R), P(=O)R, S, S=O, SO2 or none, but at least one of them is not none; wherein R can be selected from the following groups: hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl.

6. The organic mixture according to any one of claims 1 to 5, characterized in that The organic mixture further comprises a light emitter, which is selected from phosphorescent light emitters or TADF materials.

7. The organic mixture according to claim 6, characterized in that The phosphorescent emitter is a transition metal complex comprising at least one ligand or partial ligand selected from the group consisting of: Wherein T is selected from B, Al, Ga or In; K 1’ Is a direct bond selected from NR e PR e , O, S or Se; Y 1 -Y 15 are selected from C or N; Y' is selected from BR e NR e PR e ,O,S,Se,C=O,C=S,C=Se,C=NR e 、C=CR e R f 、S=O、SO2、CR e R f 、P(O)R e 、SiR e R f or GeR e R f ; R e and R f Can be fused or linked to form a ring; R a 、R b 、R c and R d are represented as a single to the maximum possible number of substituents or unsubstituted, respectively; R a1 、R b1 、R c1 、R d1 、R a 、R b 、R c 、R d 、R e and R f are independently selected from H, D, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boron, arylalkyl, alkoxy, alkenyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfonamide, sulfoxide, phosphorus, seleno or a combination of these groups; and R a1 、R b1 、R c1 、R d1 、R a 、R b 、R c 、R d Any two adjacent substituents may be fused or linked to form a ring or to form a multidentate ligand.

8. A composition comprising an organic mixture according to any one of claims 1 to 7, and at least one organic solvent.

9. An organic compound having a structure represented by chemical formula (II-1), characterized in that: The L does not contain a cyano group, and L is selected from the following electron-withdrawing groups, which may be further substituted with any substitution: where X 1 -X 8 Selected from CR or N, and at least one of them is N; Z1, Z2, and Z3 independently represent N(R), C(R)2, Si(R)2, O, C=N(R), C=C(R)2, P(R), P(=O)R, S, S=O, SO2 or none, but at least one of them is not none; wherein R can be selected from the following groups: hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl.

10. The organic compound according to claim 9, characterized in that Having any one of the chemical formulas (II-1a) to (II-1e):

11. A photovoltaic device comprising an organic mixture according to any one of claims 1 to 7 or an organic compound according to any one of claims 9 to 10.