Boron-containing organic compound and organic electroluminescent device prepared from same

Abstract

The invention discloses a boron-containing organic compound and an organic electroluminescent device prepared from the same, and belongs to the technical field of semiconductors. The structure of the organic compound is shown as a general formula (1), # imgabs0, and the compound provided by the invention has narrow half-peak width and high fluorescence quantum yield, and can be used as a luminescent layer green light doping material of an organic electroluminescent device, so that the luminescent color purity and efficiency of the device are improved.

Description

[0001] This invention application is based on the divisional application of the prior application number: 2023101970803, the application date: March 02, 2023, and the invention name: A boron-containing organic compound and an organic electroluminescent device prepared therefrom. Technical Field

[0002] The present invention relates to the field of semiconductor technology, and in particular to a boron-containing organic compound as an OLED doping material and an organic electroluminescent device containing the same. Background Art

[0003] Traditional fluorescent doped materials are limited by early technologies and can only use 25% of singlet excitons formed by electrical excitation to emit light. The internal quantum efficiency of the device is low (up to 25%), and the external quantum efficiency is generally less than 5%, which is far behind the efficiency of phosphorescent devices. Since the strong spin-orbit coupling of the heavy atom center enhances intersystem crossing, phosphorescent materials can effectively use singlet and triplet excitons formed by electrical excitation to emit light, making the internal quantum efficiency of the device reach 100%. However, most phosphorescent materials are expensive, have poor material stability, poor color purity, and serious device efficiency roll-off, which limits their application in OLEDs.

[0004] With the advent of the 5G era, higher requirements are placed on color rendering standards. In addition to being efficient and stable, luminescent materials also require a narrower half-width to improve the purity of the device's luminescent color. Fluorescent doped materials can achieve high fluorescence quantum and narrow half-width through molecular engineering. Blue fluorescent doped materials have achieved a phased breakthrough, and the half-width of boron materials can be reduced to below 30nm. In the green light region, which is more sensitive to the human eye, research is mainly focused on phosphorescent doped materials, but their luminescent peak shape is difficult to narrow by simple methods. Therefore, in order to meet higher color rendering standards, it is of great significance to study efficient green fluorescent doped materials with narrow half-width.

[0005] In addition, the sensitization technology combines triplet exciton-sensitizing materials with fluorescent doping materials, uses triplet exciton-sensitizing materials as exciton-sensitizing media, makes full use of triplet excitons, and transfers energy to fluorescent doping materials through energy transfer, which can also achieve 100% device quantum efficiency. This technology can make up for the shortcomings of insufficient exciton utilization of fluorescent doping materials, and effectively give play to the characteristics of high fluorescence quantum yield, high device stability, high color purity and low price of fluorescent doping materials, and has broad prospects in OLEDs applications.

[0006] Boron compounds with a resonant structure are more likely to achieve narrow half-width luminescence. Such materials are used in sensitization technology to achieve the preparation of devices with high efficiency and narrow half-width emission. For example, CN 107507921 A and CN 110492006A disclose a luminescent layer combination technology with a TADF material having a difference between the lowest singlet and the lowest triplet energy level of less than or equal to 0.2eV as the main body and a boron-containing material as the doping; CN 110492005 A and CN 110492009A disclose a luminescent layer combination scheme with an exciplex as the main body and a boron-containing material as the doping; both can achieve efficiency comparable to phosphorescence and a relatively narrow half-width. Therefore, the development of sensitization technology based on narrow half-width boron-based luminescent materials has unique advantages and strong potential in terms of BT.2020 display indicators. Summary of the invention

[0007] In view of the above problems existing in the prior art, the present invention application provides a boron-containing organic compound and an organic electroluminescent device prepared therefrom. The compound of the present invention has a narrow half-width and a high fluorescence quantum yield, and can be used as a green light doping material for the light-emitting layer of the organic electroluminescent device, thereby improving the luminescent color purity and life of the device.

[0008] The technical solution of the present invention is as follows: a boron-containing organic compound, the structure of which is shown in general formula (1):

[0009]

[0010] In the general formula (1), A1 and A2 are each independently a substituted or unsubstituted C6-C 30 aryl, substituted or unsubstituted C2-C 30 One of the heteroaryl groups;

[0011] X represents O, S, N(R1), C(R2)(R3) or Si(R4)(R5); Z1 represents C-R6;

[0012] R1, R2, R3, R4, and R5 are independently substituted or unsubstituted C1-C 10 Alkyl, substituted or unsubstituted C3~C 10 Cycloalkyl, substituted or unsubstituted C1~C 10 Alkoxy, substituted or unsubstituted C6~C 10 Aryloxy, substituted or unsubstituted C6~C 30 Aryl, substituted or unsubstituted C2~C 30 One of the heteroaryl groups; R1 can also be connected with A1 to form a ring;

[0013] A3 is represented by the structure shown in general formula (2):

[0014]

[0015] In the general formula (2), Z2 is represented by C-R7;

[0016] R6 and R7 are the same or different when they appear each time and represent hydrogen atoms, deuterium atoms, halogen atoms, substituted or unsubstituted C1-C 10 Alkyl, substituted or unsubstituted C3~C 10 Cycloalkyl, substituted or unsubstituted C1~C 10 Alkoxy, substituted or unsubstituted C6~C 10 Aryloxy, substituted or unsubstituted arylamine, substituted or unsubstituted C6~C 30 Aryl, substituted or unsubstituted C2~C 30 One of the heteroaryl groups;

[0017] The substituents for the substituent groups are selected from deuterium atoms, halogen atoms, cyano groups, C1-C 10 Alkyl, C3-C 10 Cycloalkyl, C6-C 30 Aryl, C2-C 30 One or more of heteroaryl and amine;

[0018] The heteroatom in the heteroaryl group is selected from one or more of oxygen, sulfur, nitrogen and silicon atoms.

[0019] In a preferred embodiment, the structure of the organic compound is any one of the general formula (3) and the general formula (4):

[0020]

[0021] In the general formula (3) and the general formula (4), A1, A2, X, Z1 and Z2 have the same meanings as defined above.

[0022] In a preferred embodiment, the structure of the organic compound is shown in general formula (II-1) to general formula (II-10):

[0023]

[0024]

[0025] In general formula (II-1) to general formula (II-10), the meanings of A1, A2, Z1, Z2, R1, R2, R3, R4, and R5 are the same as defined above.

[0026] In a preferred embodiment, the structure of the organic compound is any one of the general formula (3-1) and the general formula (4-1):

[0027]

[0028] In the general formula (3-1) and the general formula (4-1), X, Z1, and Z2 have the same meanings as defined above;

[0029] Z3 is represented by CR;

[0030] R represents a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted C1-C 10 Alkyl, substituted or unsubstituted C3~C 10 Cycloalkyl, substituted or unsubstituted C1~C 10 Alkoxy, substituted or unsubstituted C6~C 10 Aryloxy, substituted or unsubstituted arylamine, substituted or unsubstituted C6~C 30 Aryl, substituted or unsubstituted C2~C 30 One of the heteroaryl groups;

[0031] The substituents for the substituent groups are selected from deuterium atoms, halogen atoms, cyano groups, C1-C 10 Alkyl, C3-C 10 Cycloalkyl, C6-C 30 Aryl, C2-C 30 One or more of heteroaryl and amine;

[0032] The heteroatom in the heteroaryl group is selected from one or more of oxygen, sulfur, nitrogen and silicon atoms.

[0033] In a preferred embodiment, the structure of the organic compound is any one of the general formulas (III-1) to (III-4):

[0034]

[0035] In general formula (III-1) to general formula (III-4), Z1 is represented by C-R6;

[0036] Z2 is represented by C-R7; Z3 is represented by CR;

[0037] R6, R7, and R each appearing the same or different represent hydrogen atoms, deuterium atoms, halogen atoms, substituted or unsubstituted C1-C 10 Alkyl, substituted or unsubstituted C3~C 10 Cycloalkyl, substituted or unsubstituted C1~C 10 Alkoxy, substituted or unsubstituted C6~C 10 Aryloxy, substituted or unsubstituted arylamine, substituted or unsubstituted C6~C 30 Aryl, substituted or unsubstituted C2~C 30 One of the heteroaryl groups;

[0038] X represents O, S, N(R1), C(R2)(R3) or Si(R4)(R5);

[0039] R1, R2, R3, R4, and R5 are independently substituted or unsubstituted C1-C 10 Alkyl, substituted or unsubstituted C3~C 10 Cycloalkyl, substituted or unsubstituted C1~C 10 Alkoxy, substituted or unsubstituted C6~C 10 Aryloxy, substituted or unsubstituted C6~C 30 Aryl, substituted or unsubstituted C2~C 30 One of the heteroaryl groups;

[0040] R a , R b , R c , R d , R e , R f Each independently represents a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a substituted or unsubstituted C1-C 10 Alkyl, substituted or unsubstituted C3~C 10 Cycloalkyl, substituted or unsubstituted C1~C 10 Alkoxy, substituted or unsubstituted C6~C 10 Aryloxy, substituted or unsubstituted arylamine, substituted or unsubstituted C6~C 30 Aryl, substituted or unsubstituted C2~C 30 One of the heteroaryl groups;

[0041] The substituents for the substituent groups are selected from deuterium atoms, halogen atoms, cyano groups, C1-C 10 Alkyl, C3-C 10 Cycloalkyl, C6-C 30 Aryl, C2-C 30 One or more of heteroaryl and amine;

[0042] The heteroatom in the heteroaryl group is selected from one or more of oxygen, sulfur, nitrogen and silicon atoms.

[0043] In a preferred embodiment, R1, R2, R3, R4, and R5 are independently represented by adamantyl, methyl, deuterated methyl, trifluoromethyl, ethyl, deuterated ethyl, isopropyl, deuterated isopropyl, tert-butyl, deuterated tert-butyl, cyclopentyl, deuterated cyclopentyl, methyl-substituted cyclopentyl, cyclohexyl, phenyl, deuterated phenyl, biphenyl, deuterated biphenyl, terphenyl, deuterated terphenyl, diphenyl ether, methyl-substituted diphenyl ether, naphthyl, anthracenyl, phenanthryl, pyridyl, phenyl-substituted pyridyl, quinolyl, furanyl, thienyl, benzofuranyl, dibenzofuranyl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, 9,9-dimethylfluorenyl, spirofluorenyl, methyl one of phenyl substituted with methyl, phenyl substituted with ethyl, phenyl substituted with isopropyl, phenyl substituted with tert-butyl, phenyl substituted with methyl, phenyl substituted with ethyl, phenyl substituted with isopropyl, tert-butyl, deuterated methyl, deuterated ethyl, phenyl substituted with isopropyl, deuterated tert-butyl, deuterated methyl, deuterated ethyl, deuterated isopropyl, deuterated tert-butyl, deuterated tert-butyl-substituted dibenzofuranyl, tert-butyl substituted with phenyl, xanthone, phenyl substituted triazine, phenyl substituted boryl, methoxy and tert-butoxy;

[0044] R6, R7, R, R a , R b , R c , R d , R e , R fand n is a hydrogen atom, a deuterium atom, a halogen atom, an adamantyl group, a methyl group, a deuterated methyl group, a trifluoromethyl group, an ethyl group, a deuterated ethyl group, an isopropyl group, a deuterated isopropyl group, a tert-butyl group, a deuterated tert-butyl group, a cyclopentyl group, a deuterated cyclopentyl group, a methyl-substituted cyclopentyl group, a cyclohexyl group, a phenyl group, a deuterated phenyl group, a biphenyl group, a deuterated biphenyl group, a terphenyl group, a deuterated terphenyl group, a diphenyl ether group, a methyl-substituted diphenyl ether group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, a pyridyl group, a phenyl-substituted pyridyl group, a quinolyl group, a furanyl group, a thienyl group, a benzofuranyl group, a dibenzofuranyl group, a dibenzothienyl group, a carbazolyl group, an N-phenylcarbazolyl group, a 9,9-dimethylfluorenyl group, a spirofluorenyl group, a methyl-substituted phenyl group, an ethyl-substituted phenyl group, an isopropyl-substituted The invention can be selected from the group consisting of phenyl, tert-butyl-substituted phenyl, methyl-substituted biphenyl, ethyl-substituted biphenyl, isopropyl-substituted biphenyl, tert-butyl-substituted biphenyl, deuterated methyl-substituted phenyl, deuterated ethyl-substituted phenyl, deuterated isopropyl-substituted phenyl, deuterated tert-butyl-substituted phenyl, deuterated methyl-substituted biphenyl, deuterated ethyl-substituted biphenyl, deuterated isopropyl-substituted biphenyl, deuterated tert-butyl-substituted biphenyl, phenyl-substituted amino, tert-butylbenzene-substituted amino, tert-butyl-substituted dibenzofuranyl, phenyl-substituted tert-butyl, xanthone, phenyl-substituted triazinyl, phenyl-substituted boryl, methoxy, tert-butoxy, diphenyl-substituted triazinyl, and diphenylamine.

[0045] In a preferred embodiment, the specific structural formula of the organic compound is any one of the following structures:

[0046]

[0047]

[0048]

[0049]

[0050]

[0051]

[0052]

[0053]

[0054]

[0055]

[0056]

[0057] An organic electroluminescent device comprises a cathode and an anode, and an organic light-emitting functional layer therebetween. The organic light-emitting functional layer comprises a light-emitting layer, and the light-emitting layer contains the boron-containing organic compound.

[0058] In a preferred embodiment, the light-emitting layer comprises a main material and a doping material, and the doping material contains the boron-containing organic compound.

[0059] In a preferred embodiment, the light-emitting layer comprises a first main material, a second main material and a doping material, at least one of the first main material and the second main material is a TADF material, and the doping material is the boron-containing organic compound.

[0060] In a preferred embodiment, the light-emitting layer comprises a host material, an exciton-sensitizing material and a doping material, wherein the exciton-sensitizing material is a complex containing a metal element, and the doping material is the boron-containing organic compound.

[0061] The beneficial technical effects of the present invention are:

[0062] (1) The compounds of the present invention are applied to OLED devices and can be used as doping materials for light-emitting layer materials. They can emit green fluorescence under the action of an electric field and can be applied to OLED lighting or OLED display fields;

[0063] (2) The compound of the present invention has a high fluorescence quantum efficiency as a doping material, and the fluorescence quantum efficiency of the material is close to 100%;

[0064] (3) The compound of the present invention is used as a doping material, and a phosphorescent material is introduced as an exciton sensitizer, which can effectively improve the device life;

[0065] (4) The spectral FWHM of the compound of the present invention is relatively narrow, which can effectively improve the color gamut of the device and improve the luminous efficiency of the device. BRIEF DESCRIPTION OF THE DRAWINGS

[0066] Figure 1 This is a schematic diagram of the structure of an OLED device in which the materials listed in the present invention are applied;

[0067] Among them, 1 is a transparent substrate layer, 2 is an anode layer, 3 is a hole injection layer, 4 is a hole transport layer, 5 is an electron blocking layer, 6 is a light-emitting layer, 7 is a hole blocking layer, 8 is an electron transport layer, 9 is an electron injection layer, and 10 is a cathode layer. DETAILED DESCRIPTION

[0068] The technical solutions in the embodiments of the present invention will be described clearly and completely below in conjunction with the drawings in the embodiments of the present invention. In the absence of conflict, the embodiments of the present invention and the features in the embodiments can be combined with each other. The present invention will be further described below in conjunction with the drawings and specific embodiments, but they are not intended to limit the present invention.

[0069] In the present invention, when describing electrodes and organic electroluminescent devices, as well as other structures, the words "upper", "lower", "top" and "bottom" used to indicate orientation only indicate the orientation in a certain state, and do not mean that the related structure can only exist in the orientation described; on the contrary, if the structure can change its position, such as inverted, the orientation of the structure will be changed accordingly. Specifically, in the present invention, the "bottom" or "lower" side of the electrode refers to the side of the electrode close to the substrate during the preparation process, and the opposite side away from the substrate is the "top" or "upper" side.

[0070] In the present invention, the substituted or unsubstituted C6-C 30 Aryl and / or substituted or unsubstituted C2-C 30 The heteroaryl group refers to substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted tetraphenyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted para-terphenyl, substituted or unsubstituted meta-terphenyl, substituted or unsubstituted substituted or unsubstituted triphenylene, substituted or unsubstituted perylene, substituted or unsubstituted indenyl, substituted or unsubstituted furyl, substituted or unsubstituted thienyl, substituted or unsubstituted pyrrolyl, substituted or unsubstituted pyrazolyl, substituted or unsubstituted imidazolyl, substituted or unsubstituted triazolyl, substituted or unsubstituted oxazolyl, substituted or unsubstituted thiazolyl, substituted or unsubstituted oxadiazolyl, substituted or unsubstituted thiadiazolyl, substituted or unsubstituted pyridinyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted triazinyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothiophenyl, substituted or unsubstituted benzimidazolyl, substituted or unsubstituted indolyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted naphthyridinyl, substituted or unsubstituted benzoxazinyl, substituted or unsubstituted benzothiazinyl, substituted or unsubstituted acridinyl, substituted or unsubstituted phenazinyl, substituted or unsubstituted phenathiazinyl, substituted or unsubstituted phenoxazinyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted carbazolyl, combinations thereof, or condensed rings of combinations of the foregoing groups, but are not limited thereto.

[0071] The C1-C10 Alkyl (including straight-chain alkyl and branched alkyl) refers to methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, isobutyl, sec-butyl, neopentyl, n-pentyl, isopentyl, octyl, heptyl, n-decyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 1-butylpentyl and the like, but is not limited thereto.

[0072] The halogen atom described in the present invention refers to a chlorine atom, a fluorine atom or a bromine atom, but is not limited thereto.

[0073] The C3-C 10 Cycloalkyl refers to a monovalent monocyclic saturated hydrocarbon group including 3 to 10 carbon atoms as ring atoms. In this article, C4-C9 cycloalkyl is preferably used, C5-C8 cycloalkyl is more preferably used, and C5-C7 cycloalkyl is particularly preferably used. Non-limiting examples thereof may include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4,4-dimethylcyclohexyl, adamantyl and cycloheptyl, but are not limited thereto.

[0074] As the substrate of the organic electroluminescent device of the present invention, any substrate commonly used in organic electroluminescent devices can be used. Examples are transparent substrates such as glass or transparent plastic substrates; opaque substrates such as silicon substrates; flexible PI film substrates. Different substrates have different mechanical strengths, thermal stability, transparency, surface smoothness, and waterproofness. Depending on the properties of the substrate, its use direction is different. In the present invention, a transparent substrate is preferably used. The thickness of the substrate is not particularly limited.

[0075] A first electrode is formed on a substrate, and the first electrode and the second electrode may be opposite to each other. The first electrode may be an anode. The first electrode may be a transmissive electrode, a semi-transmissive electrode or a reflective electrode. When the first electrode is a transmissive electrode, it may be formed using a transparent metal oxide, such as indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO) or indium tin zinc oxide (ITZO). When the first electrode is a semi-transmissive electrode or a reflective electrode, it may include Ag, Mg, Al, Pt, Pd, Au, Ni, Nd, Ir, Cr or a metal mixture. The thickness of the first electrode layer depends on the material used, and is typically 50-500nm, preferably 70-300nm and more preferably 100-200nm.

[0076] The organic functional material layer disposed between the first electrode and the second electrode includes, from bottom to top, a hole transport region, a light emitting layer and an electron transport region.

[0077] Herein, the hole transport region constituting the organic electroluminescent device can be exemplified by a hole injection layer, a hole transport layer, an electron blocking layer, and the like.

[0078] As the material for the hole injection layer, the hole transport layer, and the electron blocking layer, any material can be selected from known related materials used for OLED devices.

[0079] Examples of the above materials include phthalocyanine derivatives, triazole derivatives, triarylmethane derivatives, triarylamine derivatives, oxazole derivatives, oxadiazole derivatives, hydrazone derivatives, stilbene derivatives, pyridoline derivatives, polysilane derivatives, imidazole derivatives, phenylenediamine derivatives, amino-substituted quilone derivatives, styryl anthracene derivatives, styrylamine derivatives and the like, fluorene derivatives, spirofluorene derivatives, silazane derivatives, aniline copolymers, porphyrin compounds, carbazole derivatives, polyarylalkane derivatives, polyphenylene vinyl and its derivatives, polythiophene and its derivatives, poly-N-vinylcarbazole derivatives, thiophene oligomers and the like, conductive polymer oligomers, aromatic tertiary amine compounds, styrene amination compounds, compounds, triamines, tetraamines, benzidines, propargyl diamine derivatives, p-phenylenediamine derivatives, m-phenylenediamine derivatives, 1,1'-bis(4-diarylaminophenyl)cyclohexane, 4,4'-bis(diarylamino)biphenyls, bis[4-(diarylamino)phenyl]methanes, 4,4'-bis(diarylamino)terphenyls, 4,4'-bis(diarylamino)quaterphenyls, 4,4'-bis(diarylamino)diphenyl ethers, 4,4'-bis(diarylamino)diphenylsulfanes, bis[4-(diarylamino)phenyl]dimethylmethanes, bis[4-(diarylamino)phenyl]-bis(trifluoromethyl)methanes, or 2,2-diphenylethylene compounds.

[0080] Furthermore, according to the device matching requirements, the hole transport film layer between the hole transport auxiliary layer and the hole injection layer constituting the organic electroluminescent device can be a single film layer or a superposition structure of multiple hole transport materials. In this article, for the above-mentioned hole carrier conduction film layers with different functions, their film thickness is not particularly limited.

[0081] The hole injection layer contains a main organic material that can conduct holes, and also contains a P-type dopant material with a deep HOMO energy level (the corresponding LUMO energy level will also be very deep). Based on empirical summary, in order to achieve smooth injection of holes from the anode to the organic film layer, the HOMO energy level of the main organic material that conducts holes used in the anode interface buffer layer must have certain characteristics with the P-doped material, so that the charge transfer state between the main material and the dopant material can be realized, the ohmic contact between the buffer layer and the anode can be achieved, and the efficient injection from the electrode to the hole injection conduction can be achieved.

[0082] In view of the above empirical summary, for hole-type host materials with different HOMO energy levels, different P-doped materials need to be selected to match them in order to achieve ohmic contact at the interface and improve the hole injection effect.

[0083] Therefore, in one embodiment of the present invention, in order to better inject holes, the hole injection layer also includes a P-type doping material with charge conductivity selected from the following: quinone derivatives, such as tetracyanoquinodimethane (TCNQ) and 2,3,5,6-tetrafluoro-tetracyano-1,4-benzoquinodimethane (F4-TCNQ); or hexaazatriphenylene derivatives, such as 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HAT-CN); or cyclopropane derivatives, such as 4,4',4"-((1E,1'E,1"E)-cyclopropane-1,2,3-trimethylenetris(cyanoformyl))tris(2,3,5,6-tetrafluorobenzyl); or metal oxides, such as tungsten oxide and molybdenum oxide, but not limited to these.

[0084] In the hole injection layer of the present invention, the ratio of the hole transport material to the P-type doping material used is 99:1-95:5, preferably 99:1-97:3, based on mass.

[0085] The thickness of the hole injection layer of the present invention may be 5-100 nm, preferably 5-50 nm, and more preferably 5-20 nm, but the thickness is not limited to this range.

[0086] The thickness of the hole transport layer of the present invention may be 5 to 200 nm, preferably 10 to 150 nm, and more preferably 20 to 100 nm, but the thickness is not limited to this range.

[0087] The thickness of the electron blocking layer of the present invention may be 1-50 nm, preferably 5-30 nm, but the thickness is not limited to this range.

[0088] After forming the hole injection layer, the hole transport layer and the electron blocking layer, a corresponding light emitting layer is formed on the electron blocking layer.

[0089] The light-emitting layer may include a host material and a dopant material. The host material may be a common green light host material in the art, and the dopant material may be a boron-containing organic compound represented by the general formula (1) of the present invention.

[0090] In the light-emitting layer of the present invention, the ratio of the host material to the doping material used is 99:1-70:30, preferably 99:1-85:15 and more preferably 97:3-87:13, based on mass.

[0091] The thickness of the light-emitting layer can be adjusted to optimize the light-emitting efficiency and the driving voltage. The preferred thickness range is 5 nm to 50 nm, more preferably 10-50 nm, and more preferably 15-30 nm, but the thickness is not limited to this range.

[0092] In the present invention, the electron transport region may include, from bottom to top, a hole blocking layer, an electron transport layer, and an electron injection layer disposed on the light emitting layer, but is not limited thereto.

[0093] The hole blocking layer is a layer that blocks the holes injected from the anode from passing through the light-emitting layer and entering the cathode, thereby extending the life of the device and improving the efficiency of the device. The hole blocking layer of the present invention can be arranged on the light-emitting layer. As the hole blocking layer material of the organic electroluminescent device of the present invention, compounds with hole blocking effects known in the prior art can be used, for example, phenanthroline derivatives such as bathocuproin (referred to as BCP), metal complexes of hydroxyquinoline derivatives such as aluminum (III) bis (2-methyl-8-quinoline) -4-phenylphenolate (BAlq), various rare earth complexes, oxazole derivatives, triazole derivatives, triazine derivatives, 9,9'-(5-(6-([1,1'-biphenyl]-4-yl)-2-phenylpyrimidin-4-yl)-1,3-phenylene)bis (9H-carbazole) (CAS No.: 1345338-69-3) and other pyrimidine derivatives. The thickness of the hole blocking layer of the present invention may be 2-200 nm, preferably 5-150 nm, and more preferably 10-100 nm, but the thickness is not limited to this range.

[0094] The electron transport layer may be disposed on the light emitting layer or (if present) the hole blocking layer. The electron transport layer material is a material that easily receives electrons from the cathode and transfers the received electrons to the light emitting layer. Preferably, the material has a high electron mobility. As the electron transport layer of the organic electroluminescent device of the present invention, the electron transport layer materials for organic electroluminescent devices known in the prior art can be used, for example, metal complexes of hydroxyquinoline derivatives represented by Alq3, BAlq and Liq, various rare earth metal complexes, triazole derivatives, 2,4-bis(9,9-dimethyl-9H-fluorene-2-yl)-6-(naphthalene-2-yl)-1,3,5-triazine (CAS No.: 1459162-51-6) and other triazine derivatives, 2-(4-(9,10-di(naphthalene-2-yl)anthracene-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole (CAS No.: 561064-11-7, commonly known as LG201) and other imidazole derivatives, oxadiazole derivatives, thiadiazole derivatives, carbodiimide derivatives, quinoxaline derivatives, phenanthroline derivatives, silicon-based compound derivatives, etc. The thickness of the electron transport layer of the present invention may be 10-80 nm, preferably 20-60 nm, and more preferably 25-45 nm, but the thickness is not limited to this range.

[0095] The electron injection layer may be disposed above the electron transport layer. The electron injection layer material is generally preferably a material having a low work function so that electrons are easily injected into the organic functional material layer. As the electron injection layer material of the organic electroluminescent device of the present invention, the electron injection layer material for organic electroluminescent devices known in the prior art can be used, for example, lithium; lithium salts such as 8-hydroxyquinoline lithium, lithium fluoride, lithium carbonate or lithium azide; or cesium salts, cesium fluoride, cesium carbonate or cesium azide. The thickness of the electron injection layer of the present invention may be 0.1-5 nm, preferably 0.5-3 nm and more preferably 0.8-1.5 nm, but the thickness is not limited to this range.

[0096] The second electrode may be disposed above the electron transport region. The second electrode may be a cathode. The second electrode may be a transmissive electrode, a semi-transmissive electrode or a reflective electrode. When the second electrode is a transmissive electrode, the second electrode may include, for example, Li, Yb, Ca, LiF / Ca, LiF / Al, Al, Mg, BaF, Ba, Ag, or a compound or mixture thereof; when the second electrode is a semi-transmissive electrode or a reflective electrode, the second electrode may include Ag, Mg, Yb, Al, Pt, Pd, Au, Ni, Nd, Ir, Cr, Li, Ca, LiF / Ca, LiF / Al, Mo, Ti, or a compound or mixture thereof, but is not limited thereto. The thickness of the cathode depends on the material used, and is typically 10-50 nm, preferably 15-20 nm.

[0097] The organic electroluminescent device of the present invention may further include an encapsulation structure. The encapsulation structure may be a protective structure that prevents foreign substances such as moisture and oxygen from entering the organic layer of the organic electroluminescent device. The encapsulation structure may be, for example, a can, such as a glass can or a metal can; or a thin film covering the entire surface of the organic layer.

[0098] The method for preparing the organic electroluminescent device of the present invention comprises laminating an anode, a hole injection layer, a hole transport layer, an electron blocking layer, an organic film layer, an electron transport layer, an electron injection layer and a cathode successively on a substrate, and optionally a covering layer. In this regard, vacuum deposition, vacuum evaporation, spin coating, casting, LB method, inkjet printing, laser printing or LITI methods can be used, but are not limited thereto. In the present invention, it is preferred to use a vacuum evaporation method to form the various layers. Those skilled in the art can conventionally select various process conditions in the vacuum evaporation method according to actual needs.

[0099] The raw materials involved in the synthesis examples of the present invention can be purchased from the market or prepared by conventional preparation methods in the art;

[0100] Example 1 Synthesis of Compound 8:

[0101]

[0102] Under nitrogen protection, 10 mmol of raw material A-1, 10 mmol of N-chlorosuccinimide (NCS), 20 mL of acetonitrile, and 1 mmol of thiourea were added to a three-necked flask and stirred at room temperature for 2 hours. After the reaction, the reaction solution was concentrated and separated by column chromatography to obtain intermediate a-1. LC-MS: Measured value: 208.13 ([M+H] + ), theoretical value: 207.08.

[0103] 10mmol intermediate a-1, 10mmol raw material B-1, 1.0mmol Cu powder, 20mmol K2CO3, 20mmol Na2SO4 and 50ml 1,2-dichlorobenzene were added to a three-necked flask, heated to 190°C, and stirred for 12 hours. After the reaction was completed, 1,2-dichlorobenzene was removed, the organic layer was separated with dichloromethane, and then the organic phase was dried with anhydrous magnesium sulfate, the solvent was removed under reduced pressure, and the intermediate b-1 was purified by silica gel column chromatography (eluent: hexane: CH2Cl2 = 2:1). LC-MS: Measured value: 418.21 ([M+H] + ), theoretical value: 417.09.

[0104] 10mmol intermediate b-1, 1.5mmol Pd(OAc)2, 50mmol K2CO3, 10mmol BnEt3NCl, 3.5mmol PPh3 and 50ml DMA were added to a three-necked flask and stirred at 100°C for 6 hours. After the reaction was completed, DMA was removed, the organic layer was separated with dichloromethane, and then the organic phase was dried with anhydrous magnesium sulfate, the solvent was removed under reduced pressure, and intermediate c-1 was purified by silica gel column chromatography (eluent: hexane: CH2Cl2 = 2:1). LC-MS: Measured value: 338.10 ([M+H] + ), theoretical value: 337.16.

[0105] Under nitrogen protection, 10mmol intermediate c-1, 11mmol raw material C-1, 1mmol X-phos, 20mmol Cs2CO3 and a mixed solution of toluene / EtOH / H2O (80ml / 40ml / 40ml) were added to a three-necked flask, and then 0.5mmol Pd(OAc)2 was added, and the reaction was stirred at 110°C for 12 hours. After the reaction was completed, it was extracted with dichloromethane, and then the organic phase was dried with anhydrous magnesium sulfate, the solvent was removed, and the intermediate d-1 was purified by silica gel column chromatography (eluent: hexane: CH2Cl2 = 2:1). LC-MS: Measured value: 481.22 ([M+H] + ), theoretical value: 480.28.

[0106] 10 mmol of intermediate d-1, 30 mmol of triphenylphosphine and 50 ml of 1,2-dichlorobenzene were added to a three-necked flask and stirred for 12 hours. After the reaction was completed, it was extracted with dichloromethane, and then the organic phase was dried with anhydrous magnesium sulfate, the solvent was removed, and the intermediate e-1 was purified by silica gel column chromatography (eluent: hexane: CH2Cl2 = 2:1). LC-MS: Measured value: 449.31 ([M+H] + ), theoretical value: 448.29.

[0107] Under nitrogen protection, 0.90mmol of raw material D-1, 1.35mmol of intermediate e-1, 5.20mmol of K2CO3 and 20mL of DMF were added to a three-necked flask and then heated to 110°C. After stirring for 3 hours, the reaction mixture was cooled to room temperature, poured into a large amount of MeOH to produce a precipitate, filtered, and the obtained solid was washed with MeOH, and the obtained filtrate was evaporated in vacuo. The obtained residue was purified by silica gel column chromatography (eluent: PE: DCM = 5: 1) to obtain intermediate f-1. LC-MS: Measured value: 659.12 ([M+H] + ), theoretical value: 658.29.

[0108] Under nitrogen protection, 0.90mmol of raw material E-1, 1.35mmol of intermediate f-1, 5.20mmol of K2CO3 and 20mL of DMF were added to a three-necked flask and then heated to 110°C. After stirring for 3 hours, the reaction mixture was cooled to room temperature, poured into a large amount of MeOH to produce a precipitate, filtered, and the obtained solid was washed with MeOH, and the obtained filtrate was evaporated in vacuo. The obtained residue was purified by silica gel column chromatography (eluent: PE: DCM = 5: 1) to obtain intermediate g-1. LC-MS: Measured value: 729.52 ([M+H] + ), theoretical value: 728.47.

[0109] In a three-necked flask, under nitrogen protection, 2.20mmol of boron tribromide and 1.10mmol of intermediate g-1 were dissolved in 30mL of 1,2,4-trichlorobenzene. After stirring at 180°C for 20 hours, the reaction mixture was diluted with dichloromethane (50mL), and 100mL of sodium phosphate buffer solution with pH=6 was added at 0°C. The aqueous layer was separated and extracted with dichloromethane (100mL, three times). The crude product was purified by silica gel column chromatography (eluent: hexane / CH2Cl2=5 / 1) to obtain the target compound 8.

[0110] Example 2 Synthesis of Compound 34:

[0111]

[0112] 10.0mmol of raw material A-1 and 20mL of THF were added to a three-necked flask, and then at -70°C, butyl lithium (4.2mL, 2.5M hexane solution) was added dropwise. The resulting suspension was kept at -70°C for 30 minutes, bubbled with CO2 for 10min, and the clear solution was allowed to stand for 10 minutes. The solvent was then evaporated (0°C, 1mmHg), the crystalline residue was dissolved in 20mL of dry THF, and cooled to -70°C, and then tert-butyl lithium (6.2mL, 1.7M pentane solution) was added dropwise. After the resulting yellow solution was kept at -70°C for 1h, 10.0mmol of C2Cl6 was added, and then the reaction mixture was kept at -70°C for 1 hour, 1mL of water was added, and the solution was allowed to reach room temperature. Then, it was poured into NH4Cl (saturated aqueous solution, 50 mL) under stirring, 50 mL of ether was added, the organic phase was separated, washed with brine, and then dried over anhydrous magnesium sulfate, the solvent was removed, and the solid residue was purified by flash chromatography (hexane / ether=4:1) to obtain intermediate a-2. LC-MS: Measured value: 208.02 ([M+H] + ), theoretical value: 207.08.

[0113] The preparation method of intermediate b-2 is the same as that of intermediate b-1, except that intermediate a-2 is used to replace intermediate a-1 to obtain intermediate b-2. LC-MS: Measured value: 418.20 ([M+H] + ), theoretical value: 417.09.

[0114] The preparation method of intermediate c-2 is the same as that of intermediate c-1, except that intermediate b-1 is replaced by intermediate b-2 to obtain intermediate c-2. LC-MS: Measured value: 338.08 ([M+H] + ), theoretical value: 337.16.

[0115] The preparation method of intermediate d-2 is the same as that of intermediate d-1, except that intermediate c-2 is used to replace intermediate c-1 to obtain intermediate d-2. LC-MS: Measured value: 481.32 ([M+H] + ), theoretical value: 480.28.

[0116] The preparation method of intermediate e-2 is the same as that of intermediate e-1, except that intermediate d-1 is replaced by intermediate d-2 to obtain intermediate e-2. LC-MS: Measured value: 449.18 ([M+H] + ), theoretical value: 448.29.

[0117] The preparation method of intermediate f-2 is the same as that of intermediate f-1, except that intermediate e-1 is replaced by intermediate e-2, and raw material D-1 is replaced by raw material D-2 to obtain intermediate f-2. LC-MS: Measured value: 603.20 ([M+H] + ), theoretical value: 602.23.

[0118] The preparation method of intermediate g-2 is the same as that of intermediate g-1, except that intermediate f-1 is replaced by intermediate f-2 to obtain intermediate g-2. LC-MS: Measured value: 673.26 ([M+H] + ), theoretical value: 672.41.

[0119] The preparation method of compound 34 is the same as that of compound 8, except that intermediate g-2 is used to replace intermediate g-1 to obtain compound 34.

[0120] Example 3 Synthesis of Compound 43:

[0121]

[0122] The preparation method of intermediate f-3 is the same as that of intermediate f-2, except that raw material D-3 is used to replace raw material D-2 to obtain intermediate f-3. LC-MS: Measured value: 834.19 ([M+H] + ), theoretical value: 833.31.

[0123] The preparation method of intermediate g-3 is the same as that of intermediate g-1, except that intermediate f-1 is replaced by intermediate f-3 to obtain intermediate g-3. LC-MS: Measured value: 904.41 ([M+H] + ), theoretical value: 903.49.

[0124] The preparation method of compound 43 is the same as that of compound 8, except that intermediate g-3 is used to replace intermediate g-1 to obtain compound 43.

[0125] Example 4 Synthesis of Compound 60:

[0126]

[0127] The preparation method of intermediate g-4 is the same as that of intermediate g-1, except that raw material E-4 is used to replace raw material E-1 to obtain intermediate g-4. LC-MS: Measured value: 745.60 ([M+H] + ), theoretical value: 744.45.

[0128] The preparation method of compound 60 is the same as that of compound 8, except that intermediate g-4 is used to replace intermediate g-1 to obtain compound 60.

[0129] Example 5 Synthesis of Compound 86:

[0130]

[0131] The preparation method of intermediate f-5 is the same as that of intermediate f-2, except that raw material D-1 is used to replace raw material D-2 to obtain intermediate f-5. LC-MS: Measured value: 659.41 ([M+H] + ), theoretical value: 658.29.

[0132] The preparation method of intermediate g-5 is the same as that of intermediate g-2, except that intermediate f-2 is replaced by intermediate f-5, and raw material E-1 is replaced by raw material E-4 to obtain intermediate g-5. LC-MS: Measured value: 745.48 ([M+H] + ), theoretical value: 744.45.

[0133] The preparation method of compound 86 is the same as that of compound 8, except that intermediate g-5 is used to replace intermediate g-1 to obtain compound 86.

[0134] Example 6 Synthesis of Compound 112:

[0135]

[0136] The preparation method of intermediate g-6 is the same as that of intermediate g-1, except that raw material E-6 is used to replace raw material E-1 to obtain intermediate g-6. LC-MS: Measured value: 860.62 ([M+H] + ), theoretical value: 859.58.

[0137] The preparation method of compound 112 is the same as that of compound 8, except that intermediate g-6 is used to replace intermediate g-1 to obtain compound 112.

[0138] Example 7 Synthesis of Compound 121:

[0139]

[0140] The preparation method of intermediate f-7 is the same as that of intermediate f-1, except that raw material D-3 is used to replace raw material D-1 to obtain intermediate f-7. LC-MS: Measured value: 834.28 ([M+H] + ), theoretical value: 833.31.

[0141] The preparation method of intermediate g-7 is the same as that of intermediate g-1, except that intermediate f-1 is replaced by intermediate f-7, and raw material E-1 is replaced by raw material E-6 to obtain intermediate g-7. LC-MS: Measured value: 1035.44 ([M+H] + ), theoretical value: 1034.60.

[0142] The preparation method of compound 121 is the same as that of compound 8, except that intermediate g-7 is used to replace intermediate g-1 to obtain compound 121.

[0143] Example 8 Synthesis of Compound 141:

[0144]

[0145] The preparation method of intermediate g-8 is the same as that of intermediate g-5, except that raw material E-6 is used to replace raw material E-4 to obtain intermediate g-8. LC-MS: Measured value: 860.64 ([M+H] + ), theoretical value: 859.58.

[0146] The preparation method of compound 141 is the same as that of compound 8, except that intermediate g-8 is used to replace intermediate g-1 to obtain compound 141.

[0147] Example 9 Synthesis of Compound 169:

[0148]

[0149] The preparation method of intermediate g-9 is the same as that of intermediate g-1, except that raw material E-9 is used to replace raw material E-1 to obtain intermediate g-9. LC-MS: Measured value: 858.42 ([M+H] + ), theoretical value: 857.56.

[0150] The preparation method of compound 169 is the same as that of compound 8, except that intermediate g-9 is used to replace intermediate g-1 to obtain compound 169.

[0151] Example 10 Synthesis of Compound 196:

[0152]

[0153] The preparation method of intermediate g-10 is the same as that of intermediate g-5, except that raw material E-9 is used to replace raw material E-4 to obtain intermediate g-10. LC-MS: Measured value: 858.59 ([M+H] + ), theoretical value: 857.56.

[0154] The preparation method of compound 196 is the same as that of compound 8, except that intermediate g-10 is used to replace intermediate g-1 to obtain compound 196.

[0155] Example 11 Synthesis of Compound 206:

[0156]

[0157] The preparation method of intermediate g-11 is the same as that of intermediate g-3, except that raw material E-9 is used to replace raw material E-1 to obtain intermediate g-11. LC-MS: Measured value: 1033.46 ([M+H] + ), theoretical value: 1032.58.

[0158] The preparation method of compound 206 is the same as that of compound 8, except that intermediate g-1 is replaced by intermediate g-11 to obtain compound 206.

[0159] Example 12 Synthesis of Compound 233:

[0160]

[0161] The preparation method of intermediate b-3 is the same as that of intermediate b-2, except that raw material A-2 is used to replace intermediate a-2 to obtain intermediate b-3, LC-MS: measured value: 362.05, theoretical value: 361.02.

[0162] The preparation method of intermediate c-3 is the same as intermediate c-2, except that intermediate b-2 is replaced by intermediate b-3 to obtain intermediate c-3, LC-MS: measured value: 282.13, theoretical value: 281.10.

[0163] The preparation method of intermediate d-3 is the same as intermediate d-2, except that intermediate c-2 is replaced by intermediate c-3 to obtain intermediate d-3, LC-MS: measured value: 369.17, theoretical value: 368.15.

[0164] The preparation method of intermediate e-3 is the same as intermediate e-2, except that intermediate d-2 is replaced by intermediate d-3 to obtain intermediate e-3, LC-MS: measured value: 337.22, theoretical value: 336.16.

[0165] The preparation method of intermediate f-8 is the same as that of intermediate f-2, except that intermediate e-2 is replaced by intermediate e-3, and raw material D-2 is replaced by raw material D-3 to obtain intermediate f-8, LC-MS: measured value: 565.20, theoretical value: 564.16.

[0166] Under nitrogen protection, 0.90mmol of raw material E-9, 1.0mmol of intermediate f-8, 5.20mmol of K2CO3 and 20mL of DMF were added to a three-necked flask and then heated to 110°C. After stirring for 3 hours, the reaction mixture was cooled to room temperature, and the reaction mixture was poured into a large amount of MeOH to produce a precipitate. After filtration, the obtained solid was washed with MeOH, and the obtained filtrate was evaporated in vacuo. The obtained residue was purified by silica gel column chromatography (eluent: PE: DCM = 5: 1) to obtain intermediate g-12, LC-MS: measured value: 824.41, theoretical value: 823.35.

[0167] In a sealed pressure-resistant tube, under nitrogen protection, 10 mmol of intermediate g-12 and 85 mL of o-dichlorobenzene were added. 10 mmol of 2.5 M tert-butyl lithium in n-hexane was added at 0°C, the system was heated to 60°C and reacted for 4 hours, then 15 mmol of boron tribromide was added at 0°C, the reaction was continued at room temperature for 3 hours, then 20 mmol of N,N-diisopropylethylamine was added to the system at 0°C, the reaction was heated to 200°C and reacted for 12 hours. After the reaction was completed, the organic layer was decompressed and concentrated, and then purified by silica gel column chromatography to obtain compound 233.

[0168] The structural characteristics of the compounds obtained in each example are shown in Table 1

[0169] Table 1

[0170]

[0171] The compounds of the present invention are used in light-emitting devices and can be used as doping materials for light-emitting layers. The physical and chemical properties of the compounds prepared in the above embodiments of the present invention were tested, and the test results are shown in Table 2:

[0172] Table 2

[0173]

[0174]

[0175] Note: PLQY (fluorescence quantum yield) and FWHM (half-maximum width) are measured by Horiba's Fluorolog-3 series fluorescence spectrometer in the thin film state.

[0176] It can be seen from the data in Table 2 above that the compound of the present invention has a high fluorescence quantum efficiency as a doping material, and the fluorescence quantum efficiency of the material is close to 100%; at the same time, the spectral FWHM of the material is narrow, which can effectively improve the color gamut of the device and improve the luminous efficiency of the device.

[0177] The following describes in detail the application effect of the OLED material synthesized by the present invention in the device through device embodiments 1-12 and device comparative examples 1-3. The device manufacturing process of device embodiments 2-12 and device comparative examples 1-3 of the present invention is exactly the same as that of device embodiment 1, and the same substrate material and electrode material are used. The film thickness of the electrode material is also the same. The difference is that the light-emitting layer material in the device is replaced. The layer structure and test results of each device embodiment are shown in Table 3 and Table 4 respectively.

[0178] Device Example 1

[0179] like Figure 1 As shown, the transparent substrate layer 1 is a transparent PI film, and the ITO anode layer 2 (film thickness is 150nm) is washed, that is, washing with a cleaning agent (Semiclean M-L20), washing with pure water, drying, and then ultraviolet-ozone washing to remove organic residues on the surface of the transparent ITO. On the ITO anode layer 2 after the above washing, a vacuum evaporation device is used to evaporate HT-1 and HI-1 with a film thickness of 10nm as a hole injection layer 3, and the mass ratio of HT-1 and HI-1 is 97:3. Then evaporate HT-1 with a thickness of 60nm as a hole transport layer 4. Then evaporate EB-1 with a thickness of 30nm as an electron blocking layer 5. After the above electron blocking material is evaporated, the light-emitting layer 6 of the OLED light-emitting device is prepared, using GH-1 and GH-2 as the main materials, compound 8 as the doping material, the mass ratio of GH-1, GH-2 and compound 8 is 69:30:1, and the film thickness of the light-emitting layer is 30nm. After the above-mentioned light-emitting layer 6, HB-1 was vacuum-deposited to a thickness of 5 nm, which was the hole blocking layer 7. After the above-mentioned hole blocking layer 7, ET-1 and Liq were vacuum-deposited to a thickness of 30 nm, with a mass ratio of ET-1 to Liq of 1:1. On the electron transport layer 8, a LiF layer with a thickness of 1 nm was made by vacuum evaporation, which was the electron injection layer 9. On the electron injection layer 9, a Mg:Ag electrode layer with a thickness of 80 nm was made by vacuum evaporation, with a mass ratio of Mg to Ag of 1:9, which was used as the cathode layer 10.

[0180] The following describes in detail the application effect of the OLED material synthesized by the present invention in the device through device examples 13-24 and device comparison examples 4-6. The device manufacturing process of device examples 14-24 and device comparison examples 4-6 of the present invention is exactly the same as that of device example 13, and the same substrate material and electrode material are used. The film thickness of the electrode material is also the same. The difference is that the light-emitting layer material in the device is replaced. The layer structure and test results of each device embodiment are shown in Table 3 and Table 4 respectively.

[0181] Device Example 13

[0182] The transparent substrate layer 1 is a transparent PI film, and the ITO anode layer 2 (film thickness is 150nm) is washed, that is, washed with a cleaning agent (Semiclean M-L20), washed with pure water, dried, and then washed with ultraviolet-ozone to remove organic residues on the surface of the transparent ITO. On the ITO anode layer 2 after the above washing, a vacuum evaporation device is used to evaporate HT-1 and HI-1 with a film thickness of 10nm as a hole injection layer 3, and the mass ratio of HT-1 and HI-1 is 97:3. Then evaporate HT-1 with a thickness of 60nm as a hole transport layer 4. Then evaporate EB-1 with a thickness of 30nm as an electron blocking layer 5. After the above electron blocking material is evaporated, the light-emitting layer 6 of the OLED light-emitting device is prepared, using GH-1 and GH-2 as the main materials, GD-1 as the first doping material, and compound 8 as the second doping material. The mass ratio of GH-1, GH-2, GD-1 and compound 8 is 66:30:3:1, and the film thickness of the light-emitting layer is 30nm. After the above-mentioned light-emitting layer 6, HB-1 was vacuum-deposited to a thickness of 5 nm, which was the hole blocking layer 7. After the above-mentioned hole blocking layer 7, ET-1 and Liq were vacuum-deposited to a thickness of 30 nm, with a mass ratio of ET-1 to Liq of 1:1. On the electron transport layer 8, a LiF layer with a thickness of 1 nm was made by vacuum evaporation, which was the electron injection layer 9. On the electron injection layer 9, a Mg:Ag electrode layer with a thickness of 80 nm was made by vacuum evaporation, with a mass ratio of Mg to Ag of 1:9, which was used as the cathode layer 10.

[0183] The molecular structure formula of the relevant materials is shown below:

[0184]

[0185] After the OLED light emitting device is completed as described above, the anode and cathode are connected by a known driving circuit, and the voltage, current efficiency and life of the device are measured. The device examples and comparative examples prepared by the same method are shown in Table 3; the test results of the voltage, current efficiency and life of the obtained device are shown in Table 4.

[0186] Table 3

[0187]

[0188]

[0189] Table 4

[0190]

[0191]

[0192] Note: Voltage, current efficiency, and luminous peak are measured using IVL (current-voltage-luminance) test system (Suzhou Fushida Scientific Instrument Co., Ltd.); the life test system is EAS-62C OLED device life tester from Japan System Technology Co., Ltd.; LT95 refers to the time it takes for the device brightness to decay to 95%; all data are at 10mA / cm 2 Next test.

[0193] It can be seen from the device data results in Table 4 that, compared with device comparison examples 1-3, the device life of the compounds of the present invention in single-doping system devices is higher than that of the comparison examples; in single-doping system devices, the device efficiency also shows a good effect, because such boron nitrogen fused ring mother core can enhance the resonance intensity and improve the device efficiency without changing the light color; compared with device comparison examples 4-6, the compounds of the present invention are in dual-doping system devices using exciton-sensitizing materials as the first doping, the current efficiency and device life of the device are greatly improved relative to OLED devices of known materials, and in dual-doping devices, the device efficiency is also significantly improved compared to single doping.

[0194] In summary, the above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A boron-containing organic compound, characterized in that The structure of the boron-containing organic compound is shown in general formula (1): In the general formula (1), A1 and A2 are each independently a substituted or unsubstituted C6-C 30 aryl, substituted or unsubstituted C2-C 30 One of the heteroaryl groups; X represents O, S, N(R1), C(R2)(R3) or Si(R4)(R5); Z1 represents C-R6; R1, R2, R3, R4, and R5 are independently substituted or unsubstituted C1-C 10 Alkyl, substituted or unsubstituted C3~C 10 Cycloalkyl, substituted or unsubstituted C1~C 10 Alkoxy, substituted or unsubstituted C6~C 10 Aryloxy, substituted or unsubstituted C6~C 30 Aryl, substituted or unsubstituted C2~C 30 One of the heteroaryl groups; R1 can also be connected with A1 to form a ring; A3 is represented by the structure shown in general formula (2): In the general formula (2), Z2 is represented by C-R7; R6 and R7 are the same or different when they appear each time and represent hydrogen atoms, deuterium atoms, halogen atoms, substituted or unsubstituted C1-C 10 Alkyl, substituted or unsubstituted C3~C 10 Cycloalkyl, substituted or unsubstituted C1~C 10 Alkoxy, substituted or unsubstituted C6~C 10 Aryloxy, substituted or unsubstituted arylamine, substituted or unsubstituted C6~C 30 Aryl, substituted or unsubstituted C2~C 30 One of the heteroaryl groups; The substituents for the substituent groups are selected from deuterium atoms, halogen atoms, cyano groups, C1-C 10 Alkyl, C3-C 10 Cycloalkyl, C6-C 30 Aryl, C2-C 30 One or more of heteroaryl and amine; The heteroatom in the heteroaryl group is selected from one or more of oxygen, sulfur, nitrogen and silicon atoms.

2. The boron-containing organic compound according to claim 1, characterized in that The structure of the organic compound is any one of the general formula (3) and the general formula (4): In general formula (3) and general formula (4), A1, A2, X, Z1, and Z2 have the same meanings as defined in claim 1.

3. The boron-containing organic compound according to claim 1, characterized in that The structure of the organic compound is shown in general formula (II-1) to general formula (II-10): In general formula (II-1) to general formula (II-10), the meanings of A1, A2, Z1, Z2, R1, R2, R3, R4, and R5 are the same as those defined in claim 1.

4. The boron-containing organic compound according to claim 1, characterized in that The structure of the organic compound is any one of the general formula (3-1) and the general formula (4-1): In the general formula (3-1) and the general formula (4-1), X, Z1, and Z2 have the same meanings as defined in claim 1; Z3 is represented by CR; R represents a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted C1-C 10 Alkyl, substituted or unsubstituted C3~C 10 Cycloalkyl, substituted or unsubstituted C1~C 10 Alkoxy, substituted or unsubstituted C6~C 10 Aryloxy, substituted or unsubstituted arylamine, substituted or unsubstituted C6~C 30 Aryl, substituted or unsubstituted C2~C 30 One of the heteroaryl groups; The substituents for the substituent groups are selected from deuterium atoms, halogen atoms, cyano groups, C1-C 10 Alkyl, C3-C 10 Cycloalkyl, C6-C 30 Aryl, C2-C 30 One or more of heteroaryl and amine; The heteroatom in the heteroaryl group is selected from one or more of oxygen, sulfur, nitrogen and silicon atoms.

5. The boron-containing organic compound according to claim 4, characterized in that The structure of the organic compound is any one of the general formulas (III-1) to (III-4): In general formula (III-1) to general formula (III-4), Z1 is represented by C-R6; Z2 is represented by C-R7; Z3 is represented by CR; R6, R7, and R each appearing the same or different represent hydrogen atoms, deuterium atoms, halogen atoms, substituted or unsubstituted C1-C 10 Alkyl, substituted or unsubstituted C3~C 10 Cycloalkyl, substituted or unsubstituted C1~C 10 Alkoxy, substituted or unsubstituted C6~C 10 Aryloxy, substituted or unsubstituted arylamine, substituted or unsubstituted C6~C 30 Aryl, substituted or unsubstituted C2~C 30 One of the heteroaryl groups; X represents O, S, N(R1), C(R2)(R3) or Si(R4)(R5); R1, R2, R3, R4, and R5 are independently substituted or unsubstituted C1-C 10 Alkyl, substituted or unsubstituted C3~C 10 Cycloalkyl, substituted or unsubstituted C1~C 10 Alkoxy, substituted or unsubstituted C6~C 10 Aryloxy, substituted or unsubstituted C6~C 30 Aryl, substituted or unsubstituted C2~C 30 One of the heteroaryl groups; R a , R b , R c , R d , R e , R f Each independently represents a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a substituted or unsubstituted C1-C 10 Alkyl, substituted or unsubstituted C3~C 10 Cycloalkyl, substituted or unsubstituted C1~C 10 Alkoxy, substituted or unsubstituted C6~C 10 Aryloxy, substituted or unsubstituted arylamine, substituted or unsubstituted C6~C 30 Aryl, substituted or unsubstituted C2~C 30 One of the heteroaryl groups; The substituents for the substituent groups are selected from deuterium atoms, halogen atoms, cyano groups, C1-C 10 Alkyl, C3-C 10 Cycloalkyl, C6-C 30 Aryl, C2-C 30 One or more of heteroaryl and amine; The heteroatom in the heteroaryl group is selected from one or more of oxygen, sulfur, nitrogen and silicon atoms.

6. The boron-containing organic compound according to any one of claims 1 to 5, characterized in that Said R1, R2, R3, R4 and R5 are independently represented by adamantyl, methyl, deuterated methyl, trifluoromethyl, ethyl, deuterated ethyl, isopropyl, deuterated isopropyl, tert-butyl, deuterated tert-butyl, cyclopentyl, deuterated cyclopentyl, methyl substituted cyclopentyl, cyclohexyl, phenyl, deuterated phenyl, biphenyl, deuterated biphenyl, terphenyl, deuterated terphenyl, diphenyl ether, methyl substituted diphenyl ether, naphthyl, anthracenyl, phenanthryl, pyridyl, phenyl substituted pyridyl, quinolyl, furanyl, thienyl, benzofuranyl, dibenzofuranyl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, 9,9-dimethylfluorenyl, spirofluorenyl, methyl substituted substituted phenyl, ethyl substituted phenyl, isopropyl substituted phenyl, tert-butyl substituted phenyl, methyl substituted biphenyl, ethyl substituted biphenyl, isopropyl substituted biphenyl, tert-butyl substituted biphenyl, deuterated methyl substituted phenyl, deuterated ethyl substituted phenyl, deuterated isopropyl substituted phenyl, deuterated tert-butyl substituted phenyl, deuterated methyl substituted biphenyl, deuterated ethyl substituted biphenyl, deuterated isopropyl substituted biphenyl, deuterated tert-butyl substituted biphenyl, tert-butyl substituted dibenzofuranyl, phenyl substituted tert-butyl, xanthone, phenyl substituted triazine, phenyl substituted boryl, methoxy, tert-butoxy; R6, R7, R, R a , R b , R c , R d , R e , R f and n is a hydrogen atom, a deuterium atom, a halogen atom, an adamantyl group, a methyl group, a deuterated methyl group, a trifluoromethyl group, an ethyl group, a deuterated ethyl group, an isopropyl group, a deuterated isopropyl group, a tert-butyl group, a deuterated tert-butyl group, a cyclopentyl group, a deuterated cyclopentyl group, a methyl-substituted cyclopentyl group, a cyclohexyl group, a phenyl group, a deuterated phenyl group, a biphenyl group, a deuterated biphenyl group, a terphenyl group, a deuterated terphenyl group, a diphenyl ether group, a methyl-substituted diphenyl ether group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, a pyridyl group, a phenyl-substituted pyridyl group, a quinolyl group, a furanyl group, a thienyl group, a benzofuranyl group, a dibenzofuranyl group, a dibenzothienyl group, a carbazolyl group, an N-phenylcarbazolyl group, a 9,9-dimethylfluorenyl group, a spirofluorenyl group, a methyl-substituted phenyl group, an ethyl-substituted phenyl group, an isopropyl-substituted The invention can be selected from the group consisting of phenyl, tert-butyl-substituted phenyl, methyl-substituted biphenyl, ethyl-substituted biphenyl, isopropyl-substituted biphenyl, tert-butyl-substituted biphenyl, deuterated methyl-substituted phenyl, deuterated ethyl-substituted phenyl, deuterated isopropyl-substituted phenyl, deuterated tert-butyl-substituted phenyl, deuterated methyl-substituted biphenyl, deuterated ethyl-substituted biphenyl, deuterated isopropyl-substituted biphenyl, deuterated tert-butyl-substituted biphenyl, phenyl-substituted amino, tert-butylbenzene-substituted amino, tert-butyl-substituted dibenzofuranyl, phenyl-substituted tert-butyl, xanthone, phenyl-substituted triazinyl, phenyl-substituted boryl, methoxy, tert-butoxy, diphenyl-substituted triazinyl, and diphenylamine.

7. The boron-containing organic compound according to claim 1, characterized in that The specific structural formula of the organic compound is any one of the following structures:

8. An organic electroluminescent device, comprising a cathode and an anode, and an organic light-emitting functional layer therebetween, wherein the organic light-emitting functional layer comprises a light-emitting layer, characterized in that: The light-emitting layer contains the boron-containing organic compound according to any one of claims 1 to 7; Preferably, the light-emitting layer comprises a host material and a doping material, and the doping material comprises the boron-containing organic compound according to any one of claims 1 to 7.

9. The organic electroluminescent device according to claim 8, wherein the light-emitting layer comprises a first host material, a second host material and a doping material, wherein: At least one of the first main material and the second main material is a TADF material, and the doping material is the boron-containing organic compound according to any one of claims 1-7.

10. The organic light-emitting device according to claim 8, wherein the light-emitting layer comprises a host material, an exciton sensitizing material and a doping material, wherein: The exciton sensitizing material is a complex containing a metal element, and the doping material is a boron-containing organic compound according to any one of claims 1 to 7.

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