An arylamine organic compound and an organic electroluminescence device prepared by the same

Abstract

The application discloses an arylamine organic compound and an organic electroluminescent device prepared from the arylamine organic compound, and belongs to the technical field of semiconductor materials. The structure of the compound is shown in general formula (1). The organic compound has excellent hole mobility under high current density. When the arylamine organic compound is used to form a hole transport material of an organic electroluminescent device, the device efficiency can be improved and the service life of the device can be prolonged, especially the high-temperature service life of the device.

Description

Technical Field

[0001] This invention relates to the field of semiconductor materials technology, and in particular to an aromatic amine organic compound and an organic electroluminescent device prepared therefrom. Background Technology

[0002] Organic Light Emission Diodes (OLEDs) technology can be used to manufacture novel display products and lighting products, and it holds promise as a replacement for existing liquid crystal displays and fluorescent lighting, with a wide range of applications. OLEDs have a sandwich-like structure, consisting of electrode material layers and organic functional materials sandwiched between these layers. These various organic functional materials are stacked together according to their intended use to form the OLED device. As a current-carrying device, when a voltage is applied to the two electrodes of the OLED, and an electric field is used to act on the positive and negative charges in the organic functional material layers, these charges recombine in the light-emitting layer, thus generating OLED electroluminescence.

[0003] Currently, OLED display technology has been applied in smartphones, tablets, and other fields, and will further expand into large-screen applications such as televisions. However, compared with the requirements of actual product applications, the luminous efficiency, lifespan, and other performance characteristics of OLED devices still need further improvement. Research on improving the performance of OLED light-emitting devices includes: reducing the driving voltage of the device, increasing the luminous efficiency of the device, and increasing the lifespan of the device. To continuously improve the performance of OLED devices, it is necessary not only to innovate in OLED device structure and manufacturing processes, but also to continuously research and innovate OLED optoelectronic functional materials to create functional materials for higher-performance OLEDs.

[0004] Blue organic light-emitting diodes (OLEDs) have always been a weak point in the development of full-color OLEDs. To date, the efficiency and lifetime of blue light-emitting devices have been difficult to improve comprehensively. Therefore, improving the performance of these devices remains a crucial issue and challenge in this field. Currently, most blue light-emitting substrates used in the market are electron-biased. Therefore, to regulate the carrier balance of the emitting layer, the hole transport material needs to have excellent hole transport performance. Better hole injection and transport will cause the recombination region to shift away from the electron blocking layer, thus reducing luminescence at the interface and improving device performance and lifetime. Therefore, the hole transport region material is required to have high hole injection capacity, high hole mobility, high electron blocking capacity, and high electron weather resistance.

[0005] As is well known in the art, in high-temperature environments, the difference between electron mobility and hole mobility is more pronounced, resulting in blue light devices exhibiting electron-rich and hole-deficient characteristics and poor device lifetime. In order to improve the high-temperature lifetime of blue light devices, it is necessary to improve the mobility of hole transport materials, especially the mobility under high-temperature conditions. Summary of the Invention

[0006] To address the aforementioned problems in the prior art, the applicant of this invention provides an aromatic amine organic compound and an organic electroluminescent device prepared therefrom. The organic compound of this invention possesses excellent hole transport capability and thermal stability. When the aromatic amine organic compound of this invention is used to form the hole transport material of an organic electroluminescent device, it can simultaneously exhibit the effects of improved device efficiency (index) and extended lifetime, especially extending the high-temperature lifetime of the device.

[0007] The technical solution of the present invention is as follows: an aromatic amine organic compound, the structure of which is shown in general formula (1):

[0008]

[0009] In general formula (1), R1-R2 are independently represented as hydrogen atom, deuterium atom, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 5-30 heteroaryl, and are connected by single bond or cyclic ring.

[0010] Ar1-Ar2 are independently represented as single bonds, substituted or unsubstituted C6-C30 arylene groups, and substituted or unsubstituted 5-30 heteroarylene groups, respectively.

[0011] The L1-L4 are independently represented as single bonds, substituted or unsubstituted C6-C30 arylene groups, and substituted or unsubstituted 5-30 heteroarylene groups, respectively.

[0012] R3-R6 are independently represented as substituted or unsubstituted C6-C30 aryl groups and substituted or unsubstituted 5-30 heteroaryl groups, respectively.

[0013] The n and m are independently represented as the numbers 0, 1 or 2, and m + n ≥ 1;

[0014] The substituents of the above-mentioned substituted or substituted groups are selected from deuterium atoms, methyl, ethyl, tert-butyl, C6-C30 aryl or 5-30 heteroaryl groups;

[0015] The heteroatoms in the heteroaryl and heteroaryl groups are selected from one or more of oxygen, sulfur, or nitrogen atoms.

[0016] In a preferred embodiment, the structure of the organic compound is shown in any one of general formulas (1-1) to (1-2):

[0017]

[0018] In general formulas (1-1) to (1-2), R1-R2 are independently represented by hydrogen atom, deuterium atom, methyl, ethyl, tert-butyl, phenyl, naphthyl, thiophene or furanyl, and are connected by single bond or cyclic ring;

[0019] Ar1-Ar2 are independently represented as single bonds, substituted or unsubstituted C6-C30 arylene groups, and substituted or unsubstituted 5-30 heteroarylene groups, respectively.

[0020] R3-R6 are independently represented as substituted or unsubstituted C6-C30 aryl groups and substituted or unsubstituted 5-30 heteroaryl groups, respectively.

[0021] The m represents the number 1 or 2;

[0022] The substituents of the above-mentioned substituted or substituted groups are selected from deuterium atoms, methyl, ethyl, tert-butyl, C6-C30 aryl or 5-30 heteroaryl groups;

[0023] The heteroatoms in the heteroaryl and heteroaryl groups are selected from one or more of oxygen, sulfur, or nitrogen atoms.

[0024] In a preferred embodiment, the structure of the organic compound is shown in any one of general formulas (1-3) to (1-6);

[0025]

[0026] In general formulas (1-3) to (1-6), Ar1-Ar2 are independently represented as single bonds, substituted or unsubstituted C6-C30 arylene groups, or substituted or unsubstituted 5-30 heteroarylene groups;

[0027] R3-R6 are independently represented as substituted or unsubstituted C6-C30 aryl groups and substituted or unsubstituted 5-30 heteroaryl groups, respectively.

[0028] The substituents of the above-mentioned substituted or substituted groups are selected from deuterium atoms, methyl, ethyl, tert-butyl, C6-C30 aryl or 5-30 heteroaryl groups;

[0029] The heteroatoms in the heteroaryl and heteroaryl groups are selected from one or more of oxygen, sulfur, or nitrogen atoms.

[0030] In a preferred embodiment, the structure of the organic compound is shown in any one of general formulas (1-7) to (1-11):

[0031]

[0032] In general formulas (1-7) to (1-11), Ar1-Ar2 are independently represented as single bonds, substituted or unsubstituted C6-C30 arylene groups, or substituted or unsubstituted 5-30 heteroarylene groups;

[0033] R3-R6 are independently represented as substituted or unsubstituted C6-C30 aryl groups and substituted or unsubstituted 5-30 heteroaryl groups, respectively.

[0034] The substituents of the above-mentioned substituted or substituted groups are selected from deuterium atoms, methyl, ethyl, tert-butyl, C6-C30 aryl or 5-30 heteroaryl groups;

[0035] The heteroatoms in the heteroaryl and heteroaryl groups are selected from one or more of oxygen, sulfur, or nitrogen atoms.

[0036] In a preferred embodiment, R1-R2 are independently represented as hydrogen atoms, deuterium atoms, methyl, ethyl, tert-butyl, phenyl, naphthyl, thiophene, or furanyl, and are connected by single bonds or cyclic rings.

[0037] Ar1-Ar2 are independently represented as single bond, substituted or substituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted biphenylene, substituted or unsubstituted furanylene, and substituted or unsubstituted thiopheneylene, respectively.

[0038] The L1-L4 are respectively independently represented as a single bond, a substituted or substituted phenylene, a substituted or unsubstituted naphthylene, a substituted or unsubstituted biphenylene, a substituted or unsubstituted furanylene, and a substituted or unsubstituted thiopheneylene.

[0039] R3-R6 are each independently represented as one of the following: substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted diphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted furanyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted thiopheneyl, substituted or unsubstituted benzothiopheneyl, substituted or unsubstituted dibenzothiopheneyl, substituted or unsubstituted phenanthyl, substituted or unsubstituted indolecycloyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted dimethylfluorenyl, substituted or unsubstituted diphenylfluorenyl, substituted or unsubstituted carbazoyl, substituted or unsubstituted spirofluorenyl, substituted or unsubstituted indolocycloyl, 1,1,4,4-tetramethyl-1,2,3,4-tetrahydronaphthalene, and 1,4-benzodioxane.

[0040] The substituents of the above-mentioned substituted or substituted groups are selected from deuterium, methyl, ethyl, tert-butyl, phenyl, naphthyl, diphenyl, pyridyl, naphthinyl, thiophenyl, furanyl, benzothiophenyl, benzofuranyl, dibenzofuranyl, dibenzothiophenyl, fluorenyl, dimethylfluorenyl, diphenylfluorenyl, carbazoleyl, or spirofluorenyl.

[0041] In a preferred embodiment, Ar1, Ar2, L1, L2, L3, and L4 are each independently represented as a single bond or as shown in the following structure:

[0042] Any one of them;

[0043] R3-R6 are each independently represented as shown in the following structure:

[0044]

[0045] Any one of them.

[0046] In a preferred embodiment, the organic compound has any one of the following structures:

[0047]

[0048]

[0049]

[0050]

[0051]

[0052]

[0053]

[0054]

[0055]

[0056]

[0057]

[0058]

[0059]

[0060] The present invention also provides an organic electroluminescent device, which sequentially includes an anode, an organic functional layer and a cathode, wherein the organic functional layer comprises the aforementioned aromatic amine organic compound.

[0061] In a preferred embodiment, the organic electroluminescent device sequentially comprises an anode, a hole transport region, a light-emitting region, an electron transport region, and a cathode, wherein the hole transport region contains the aromatic amine organic compound.

[0062] In a preferred embodiment, the hole transport region includes a hole injection layer, a hole transport layer, and an electron blocking layer, wherein the hole transport layer contains the aromatic amine compound described above.

[0063] Preferably, the hole injection layer and the hole transport layer comprise the aromatic amine compound.

[0064] The beneficial technical effects of this invention are as follows:

[0065] (1) The structure of the aromatic amine organic compounds described in this invention has stereo asymmetry. This asymmetric structure is beneficial for the molecules to maintain a stable amorphous film phase when forming a film, thereby ensuring the physicochemical stability of the film phase and the stability of the film phase under the action of point formation, which in turn is beneficial to obtaining the lifetime stability of the device.

[0066] (2) The structural characteristics of the aromatic amine organic compounds described in this invention are beneficial to increasing the glass transition temperature of the molecules and reducing the vapor deposition temperature of the molecules. In other words, even if the molecular weight of the structure is relatively high, it can ensure a low vapor deposition temperature. This excellent performance is not only beneficial to the thermal vapor deposition of the material and controlling the thermal decomposition rate of the material, but also improves the stability of the material in device applications.

[0067] (3) The compounds of this invention have high hole mobility, which enables the application of the compounds of this invention as hole transport materials to effectively improve device efficiency and reduce device voltage. Attached Figure Description

[0068] Figure 1 This is a cross-sectional view of the organic electroluminescent device of the present invention.

[0069] In the figure, 1 represents the substrate layer; 2 represents the anode layer; 3 represents the hole injection layer; 4 represents the hole transport layer; 5 represents the electron blocking layer; 6 represents the light-emitting layer; 7 represents the hole blocking layer; 8 represents the electron transport layer; 9 represents the electron injection layer; 10 represents the cathode layer; and 11 represents the capping layer. Detailed Implementation

[0070] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. The following description of at least one exemplary embodiment is merely illustrative and is in no way intended to limit the present invention or its application or use. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0071] In this invention, when a layer or element is referred to as being "above" another layer or substrate, the layer or element may be located directly above the other layer or substrate, or there may be intermediate layers. Furthermore, it will be understood that when a layer is referred to as being "between" two layers, the layer may be the only layer between the two layers, or there may be one or more intermediate layers. The same reference numerals throughout the drawings denote the same elements.

[0072] In this invention, the terms "upper," "lower," "top," and "bottom," used to describe electrodes, organic electroluminescent devices, and other structures, indicate orientation only in a specific state and do not imply that the structure can only exist in that orientation. Conversely, if the structure can be repositioned, such as by inverting it, the orientation of the structure changes accordingly. Specifically, in this invention, the "bottom" or "lower" side of the electrode refers to the side of the electrode closer to the substrate during fabrication, while the opposite side farther from the substrate is the "top" or "upper" side.

[0073] In this specification, the term "substitution" means that one or more hydrogen atoms on a specified atom or group are replaced by a specified group, provided that the normal valence of the specified atom is not exceeded under the existing conditions.

[0074] In this specification, hole characteristics refer to the characteristics that allow holes formed in the anode to be easily injected into and transported in the light-emitting layer when an electric field is applied, due to conductivity characteristics at the highest occupied molecular orbital (HOMO) level.

[0075] In this specification, electronic characteristics refer to the characteristics that allow electrons formed in the cathode to be readily injected into and transported in the light-emitting layer when an electric field is applied, and which are attributed to conductivity characteristics based on the lowest unoccupied molecular orbital (LUMO) level.

[0076] The organic electroluminescent device of the present invention can be a bottom-emitting organic electroluminescent device, a top-emitting organic electroluminescent device, or a multilayer organic electroluminescent device, and there is no specific limitation thereto.

[0077] In the organic electroluminescent device of this invention, any substrate commonly used in organic electroluminescent devices can also be used. Examples include transparent substrates, such as glass or transparent plastic substrates; opaque substrates, such as silicon substrates; and flexible polyimide (PI) film substrates. Different substrates have different mechanical strengths, thermal stability, transparency, surface smoothness, and water resistance. Their application varies depending on their properties. In this invention, a transparent substrate is preferred. There are no particular limitations on the thickness of the substrate.

[0078] anode

[0079] Preferably, the anode can be formed on the substrate. In this invention, the anode and cathode are opposite each other. The anode can be made of a conductor with a high work function to facilitate hole injection, and can be, for example, a metal such as nickel, platinum, copper, zinc, silver or alloys thereof; a metal oxide such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); a combination of metal and metal oxide, such as ZnO and Al or ITO and Ag; a conductive polymer such as poly(3-methylthiophene), poly(3,4-(ethylene-1,2-dioxy)thiophene), and polyaniline, but is not limited thereto. The thickness of the anode depends on the material used, typically 50-500 nm, preferably 70-300 nm, and more preferably 100-200 nm.

[0080] cathode

[0081] The cathode can be made of a conductor with a low work function to facilitate electron injection, and can be, for example, a metal or alloy thereof, such as magnesium, calcium, sodium, potassium, titanium, indium, aluminum, silver, tin, and combinations thereof; multilayer materials, such as LiF / Al, Li2O / Al, and BaF2 / Ca, but not limited thereto. The thickness of the cathode depends on the material used, typically 10-50 nm, preferably 15-20 nm.

[0082] Light-emitting area

[0083] In this invention, the light-emitting region can be disposed between the anode and the cathode, and can include at least one host material and at least one guest material. Both the host and guest materials of the light-emitting region in the organic electroluminescent device of this invention can be light-emitting layer materials known in the prior art for organic electroluminescent devices. The host material can be, for example, a thiazole derivative, a benzimidazole derivative, a polydialkylfluorene derivative, or 4,4'-bis(9-carbazolyl)biphenyl (CBP). The host material can be a compound containing anthracene groups. The guest material can be, for example, a quinacridone, coumarin, rubrene, perylene and its derivatives, benzopyran derivatives, rhodamine derivatives, or aminostyrene derivatives.

[0084] In a preferred embodiment of the present invention, the luminescent region contains one or two host material compounds.

[0085] In a preferred embodiment of the present invention, the host material of the luminescent region is selected from one or more of the following compounds BH-1-BH-11:

[0086]

[0087] In this invention, the luminescent region may contain phosphorescent or fluorescent guest materials to improve the fluorescence or phosphorescence properties of the organic electroluminescent device. Specific examples of phosphorescent guest materials include metal complexes of iridium, platinum, etc., while those commonly used in the art can be used for fluorescent guest materials. In a preferred embodiment of this invention, the guest material used in the luminescent film layer is selected from one of the following compounds: BD-1 to BD-10.

[0088]

[0089] In the light-emitting region of the present invention, the ratio of the host material to the guest material is 99:1-70:30, preferably 99:1-85:15 and more preferably 97:3-87:13, based on mass.

[0090] The thickness of the light-emitting region can be 10-50 nm, preferably 15-30 nm, but the thickness is not limited to this range.

[0091] Hole transport region

[0092] In the organic electroluminescent device of the present invention, a hole transport region is disposed between the anode and the light-emitting region, and includes a hole injection layer, a hole transport layer and an electron blocking layer.

[0093] Hole injection layer

[0094] The hole injection material used in the hole injection layer (also known as the anode interface buffer layer) is a material capable of fully accepting holes from the anode at low voltages, and the highest occupied molecular orbital (HOMO) of the hole injection material is preferably a value between the work function of the anode material and the HOMO of the adjacent organic material layer. In a preferred embodiment of the invention, the hole injection layer is a mixed film layer of a host organic material and a p-type dopant. For holes to be smoothly injected from the anode into the organic film layer, the HOMO energy level of the host organic material must possess certain characteristics with the p-type dopant to facilitate charge transfer states between the host and dopant materials, achieving ohmic contact between the hole injection layer and the anode, thereby achieving efficient hole injection from the electrode to the hole injection layer. This characteristic is summarized as follows: the difference between the HOMO energy level of the host material and the LUMO energy level of the p-type dopant is ≤0.4 eV. Therefore, for hole-type host materials with different HOMO energy levels, different p-type dopant materials need to be selected to match them in order to achieve ohmic contact at the interface and improve the hole injection effect.

[0095] Preferably, specific examples of the main organic material include: metalloporphyrins, oligothiophenes, aromatic amine organic materials, hexanitrile hexaazabenzophenanthrene, quinacridone organic materials, perylene organic materials, anthraquinones, polyanilines, and polythiophene conductive polymers; but are not limited thereto.

[0096] Preferably, the p-type doped material is a charge-conducting compound selected from quinone derivatives or metal oxides, such as tungsten oxide and molybdenum oxide, but not limited thereto.

[0097] In a preferred embodiment of the present invention, the p-type doped material used is selected from any one of the following compounds P-1 to P-8:

[0098]

[0099]

[0100] In one embodiment of the present invention, the ratio of the host organic material to the P-type doped material is 99:1-95:5, preferably 99:1-97:3, based on mass.

[0101] In a preferred embodiment of the present invention, the hole injection layer is a mixed film layer of the aromatic amine organic compound and the p-type doped material of the present invention.

[0102] The thickness of the hole injection layer of the present invention can be 5-20 nm, preferably 8-15 nm, but the thickness is not limited to this range.

[0103] Hole transport layer

[0104] In the organic electroluminescent device of the present invention, a hole transport layer may be disposed above a hole injection layer. The hole transport material is a suitable material having a high hole mobility, capable of accepting holes from the anode or hole injection layer and transporting the holes to the light-emitting layer. In a preferred embodiment, the hole transport layer comprises an aromatic amine organic compound of the present invention represented by the same general formula (1) as the hole injection layer.

[0105] The thickness of the hole transport layer of the present invention can be 80, 100 or 200 nm, preferably 100-150 nm, but the thickness is not limited to this range.

[0106] Electron blocking layer

[0107] In the organic electroluminescent device of the present invention, an electron blocking layer may be disposed between the hole transport layer and the light-emitting layer, and particularly in contact with the light-emitting layer. By disposing of the electron blocking layer in contact with the light-emitting layer, hole transfer at the interface between the light-emitting layer and the hole transport layer can be precisely controlled. In one embodiment of the present invention, the electron blocking layer material is selected from carbazole-based aromatic amine derivatives. The thickness of the electron blocking layer may be 5-20 nm, preferably 8-15 nm, but the thickness is not limited to this range.

[0108] Electronic transmission area

[0109] In the organic electroluminescent device of the present invention, the electron transport region is disposed between the light-emitting region and the cathode, and includes, but is not limited to, a hole blocking layer, an electron transport layer and an electron injection layer.

[0110] Electron injection layer

[0111] An electron injection layer may be disposed between the electron transport layer and the cathode. The electron injection layer material is typically preferably a material with a low work function, allowing electrons to be easily injected into the organic functional material layer. Preferably, the electron injection layer material is an N-type metal. As the electron injection layer material for the organic electroluminescent device of the present invention, electron injection layer materials known in the art for organic electroluminescent devices can be used, such as lithium; lithium salts, such as lithium 8-hydroxyquinoline, lithium fluoride, lithium carbonate, or lithium azide; or cesium salts, such as 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.

[0112] Electron transport layer

[0113] An electron transport layer may be disposed above the light-emitting film layer or (if present) a hole-blocking layer. The electron transport layer material is one that readily receives electrons from the cathode and transfers the received electrons to the light-emitting layer. A material with high electron mobility is preferred. As the electron transport layer of the organic electroluminescent device of the present invention, electron transport layer materials known in the prior art for organic electroluminescent devices can be used, such as metal complexes of hydroxyquinoline derivatives represented by Alq3, BAlq and LiQ, various rare earth metal complexes, triazole derivatives, triazine derivatives such as 2,4-bis(9,9-dimethyl-9H-fluoren-2-yl)-6-(naphth-2-yl)-1,3,5-triazine (CAS No.: 1459162-51-6), imidazole derivatives such as 2-(4-(9,10-bis(naphth-2-yl)anthracene-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole (CAS No.: 561064-11-7, commonly known as LG201), oxadiazole derivatives, etc.

[0114] In a preferred embodiment of the invention, the electron transport layer further includes other compounds conventionally used in electron transport layers, such as Alq3, LiQ, preferably LiQ.

[0115] The thickness of the electron transport layer of the present invention can be 10-80 nm, preferably 20-60 nm, and more preferably 25-45 nm, but the thickness is not limited to this range.

[0116] Cover layer

[0117] To improve the light extraction efficiency of organic electroluminescent devices, a light extraction layer (CPL layer, also known as a capping layer) can be added to the cathode of the device. According to the principles of optical absorption and refraction, the CPL capping layer material should have a higher refractive index and a lower absorption coefficient. Any material known in the art can be used as the CPL layer material, such as Alq3 or N4,N4'-diphenyl-N4,N4'-di(9-phenyl-3-carbazolyl)biphenyl-4,4'-diamine. The thickness of the CPL capping layer is typically 5-300 nm, preferably 20-100 nm, and more preferably 40-80 nm.

[0118] The organic electroluminescent device of the present invention may further include an encapsulation structure. The encapsulation structure may be a protective structure preventing external 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 or metal can; or a thin film covering the entire surface of the organic layer.

[0119] This invention discloses a method for fabricating organic electroluminescent devices, comprising sequentially 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, and optionally a capping layer, onto a substrate. In this regard, methods such as vacuum deposition, vacuum evaporation, spin coating, casting, LB method, inkjet printing, laser printing, or LITI can be used, but are not limited thereto. In this invention, vacuum evaporation is preferably used to form the various layers. Those skilled in the art can conventionally select the various process conditions in the vacuum evaporation method according to actual needs.

[0120] Synthesis Example 1

[0121] Synthesis of intermediate F-1

[0122] Step (1)

[0123]

[0124] Step (2)

[0125]

[0126] Step (3)

[0127]

[0128] (1) Under a nitrogen atmosphere, add an aqueous solution of hydrochloric acid (15 mL concentrated hydrochloric acid and 50 mL water) to a three-necked flask, and add raw material Z-1 (0.05 mmol). Cool the mixture to 0 °C, and then add 50 mL of an aqueous solution of NaNO2 (2.4 g). After adding, place the reaction mixture at -5 °C for 30 minutes. Add the reaction mixture to 50 mL of an aqueous solution of KI (7.23 g). Then, stir the reaction mixture at room temperature overnight. Pour the reaction mixture into 300 mL of water. Extract the reaction mixture with CH2Cl2. Dry the organic phase with MgSO4 and distill to give intermediate B-1.

[0129] (2) Under a nitrogen atmosphere, 0.06 mol of intermediate B-1 was added to a three-necked flask and dissolved in a mixed solvent (300 ml toluene, 90 ml H2O). The mixture was stirred under nitrogen for 1 hour, and then 0.05 mol of starting material C-1, 0.1 mol of K2CO3, and 0.005 mol of Pd(PPh3)4 were slowly added. The mixture was heated to 90°C and reacted for 9 hours. The reaction was observed using thin-layer chromatography (TLC) until complete. After naturally cooling to room temperature, water was added to the reaction system for extraction. The mixture was separated, and the organic phase was rotary evaporated under reduced pressure until no fraction remained. The obtained substance was purified by silica gel column chromatography to obtain intermediate D-1.

[0130] (3) Add 0.06 mol of intermediate D-1 and 300 mL of anhydrous tetrahydrofuran to a three-necked flask. Cool to -78°C under nitrogen protection. Slowly add 22.4 mL of 2.6 M n-butyllithium solution and maintain this temperature while stirring for 2 h. Add 0.06 mol of raw material E-1 to this solution. After the addition is complete, react at room temperature for 2 h. Add 1 mol / L hydrochloric acid solution to the reaction solution, extract with dichloromethane, dry, concentrate, add 0.3 mL of acetic acid and 0.1 mL of concentrated hydrochloric acid to the crude product, heat under reflux for 5 h, cool, filter, recrystallize with ethanol and tetrahydrofuran, and dry to obtain intermediate F-1.

[0131] Intermediate F was prepared using a method similar to that used for synthesizing intermediate F-1, as shown in Table 1 below:

[0132] Table 1

[0133]

[0134] Example 2: Synthesis of Compound 1

[0135]

[0136] In a three-necked flask, under nitrogen protection, add 0.01 mol of raw material G-1, 0.012 mol of intermediate F-1, and 150 ml of toluene, and stir to mix. Then add 5 × 10⁻⁶ ml of toluene. -5 mol Pd2(dba)3, 5×10 -5 0.03 mol of tri-tert-butylphosphine and 0.03 mol of sodium tert-butoxide were heated to 105 °C and refluxed for 20 hours. A TLC sample was taken, showing no remaining amine compounds, indicating complete reaction. The mixture was allowed to cool naturally to room temperature, filtered, and the filtrate was rotary evaporated until no fraction remained. The filtrate was then passed through a neutral silica gel column to give compound 1. Elemental analysis of the structure (molecular formula C10) is provided. 57 H 47 Theoretical values: C, 91.77; H, 6.35; N, 1.88. Measured values: C, 90.85; H, 6.32; N, 1.86. LC-MS: Measured value: 746.07 ([M+H]) + ).

[0137] Compounds 76, 366, 382, ​​389, 363, and 392 were prepared using a method similar to that described in Example 2, with the reactants involved listed in Table 2 below:

[0138] Table 2

[0139]

[0140] Example 3: Synthesis of Compound 72

[0141]

[0142] In a three-necked flask, under nitrogen protection, add 0.012 mol of raw material H-1, 0.01 mol of raw material I-4, and 150 ml of toluene, and stir to mix. Then add 5 × 10⁻⁶ ml of toluene. -5 mol Pd2(dba)3, 5×10 -5 0.03 mol of tri-tert-butylphosphine and 0.03 mol of sodium tert-butoxide were heated to 105 °C and refluxed for 18 hours. A sample was taken and spotted onto a TLC plate, showing no remaining amine compounds, indicating that the reaction was complete. The mixture was allowed to cool naturally to room temperature, filtered, and the filtrate was rotary evaporated until no fraction remained. The filtrate was then passed through a neutral silica gel column to obtain intermediate G-6.

[0143]

[0144] In a three-necked flask, under nitrogen protection, add 0.01 mol of intermediate G-6, 0.012 mol of intermediate F-1, and 150 ml of toluene, and stir to mix. Then add 5 × 10⁻⁶ ml of toluene. -5 mol Pd2(dba)3, 5×10 -5 0.03 mol of tri-tert-butylphosphine and 0.03 mol of sodium tert-butoxide were heated to 105 °C and refluxed for 20 hours. A TLC sample was taken, showing no remaining amine compounds, indicating a complete reaction. The mixture was allowed to cool naturally to room temperature, filtered, and the filtrate was rotary evaporated until no fraction remained. The filtrate was then passed through a neutral silica gel column to give compound 72. Elemental analysis of the structure (molecular formula C) is required. 59 H 57 N): Test values: C, 91.02; H, 7.29; N, 1.68. LC-MS: Measured value: 780.35 ([M+H]) + ).

[0145] Compounds 5, 10, 55, 123, and 170 were prepared using a method similar to that in Example 3, and the reactants involved are shown in Table 3 below:

[0146] Table 3

[0147]

[0148]

[0149] Example 4: Synthesis of Compound 17

[0150] Step (1)

[0151]

[0152] Step (2)

[0153]

[0154] Step (3)

[0155]

[0156] (1) Under a nitrogen atmosphere, 0.06 mol of raw material C-2 was added to a three-necked flask and dissolved in a mixed solvent (300 ml toluene, 90 ml H2O). The mixture was stirred under nitrogen for 1 hour, and then 0.05 mol of raw material J-1, 0.1 mol of K2CO3, and 0.005 mol of Pd(PPh3)4 were slowly added. The mixture was heated to 90 °C and reacted for 9 hours. The reaction was observed using thin-layer chromatography (TLC) until it was complete. After naturally cooling to room temperature, water was added to the reaction system for extraction. The mixture was separated, and the organic phase was rotary evaporated under reduced pressure until no fraction was obtained. The obtained substance was purified by silica gel column chromatography to obtain intermediate K-1.

[0157] (2) In a three-necked flask, under nitrogen protection, add 0.01 mol of raw material H-7, 0.012 mol of intermediate K-1, and 150 ml of toluene and stir to mix. Then add 5 × 10⁻⁶ ml of toluene. -5 mol Pd2(dba)3, 5×10 -5 0.03 mol of tri-tert-butylphosphine and 0.03 mol of sodium tert-butoxide were heated to 105 °C and refluxed for 21 hours. A sample was taken and spotted onto a TLC plate, showing no remaining amine compounds, indicating that the reaction was complete. The mixture was allowed to cool naturally to room temperature, filtered, and the filtrate was rotary evaporated until no fraction remained. The filtrate was then passed through a neutral silica gel column to obtain intermediate G-13.

[0158] (2) In a three-necked flask, under nitrogen protection, add 0.01 mol of intermediate G-13, 0.012 mol of intermediate F-1, and 150 ml of toluene and stir to mix. Then add 5 × 10⁻⁶ ml of toluene. -5 mol Pd2(dba)3, 5×10 -5 0.03 mol of tri-tert-butylphosphine and 0.03 mol of sodium tert-butoxide were heated to 105 °C and refluxed for 20 hours. A TLC sample was taken, showing no remaining amine compounds, indicating complete reaction. The mixture was allowed to cool naturally to room temperature, filtered, and the filtrate was rotary evaporated until no fraction remained. The filtrate was then passed through a neutral silica gel column to give compound 17. Elemental analysis and structure (molecular formula C16) are required. 61 H 49 Theoretical values: C, 92.04; H, 6.20; N, 1.76. Measured values: C, 92.30; H, 6.21; N, 1.88. LC-MS: Measured value: 796.29 ([M+H]). + ).

[0159] Example 5: Synthesis of Compound 23

[0160] Step (1)

[0161]

[0162] Step (2)

[0163]

[0164] Step (3)

[0165]

[0166] (1) Under a nitrogen atmosphere, 0.06 mol of raw material C-3 was added to a three-necked flask and dissolved in a mixed solvent (300 ml toluene, 90 ml H2O). The mixture was stirred under nitrogen for 1 hour, and then 0.05 mol of raw material J-2, 0.1 mol of K2CO3, and 0.005 mol of Pd(PPh3)4 were slowly added. The mixture was heated to 90 °C and reacted for 8 hours. The reaction was observed using thin-layer chromatography (TLC) until it was complete. After naturally cooling to room temperature, water was added to the reaction system for extraction. The mixture was separated, and the organic phase was rotary evaporated under reduced pressure until no fraction was obtained. The obtained substance was purified by silica gel column chromatography to obtain intermediate K-2.

[0167] (2) In a three-necked flask, under nitrogen protection, add 0.01 mol of raw material H-7, 0.012 mol of intermediate K-2, and 150 ml of toluene and stir to mix. Then add 5 × 10⁻⁶ ml of toluene. -5 mol Pd2(dba)3, 5×10 -5 0.03 mol of tri-tert-butylphosphine and 0.03 mol of sodium tert-butoxide were heated to 105 °C and refluxed for 21 hours. A sample was taken and spotted onto a TLC plate, showing no remaining amine compounds, indicating that the reaction was complete. The mixture was allowed to cool naturally to room temperature, filtered, and the filtrate was rotary evaporated until no fraction remained. The filtrate was then passed through a neutral silica gel column to obtain intermediate G-14.

[0168] (3) In a 250ml three-necked flask, under nitrogen protection, add 0.01mol of intermediate G-14, 0.012mol of intermediate F-1, and 150ml of toluene, stir and mix, then add 5×10 -5 mol Pd2(dba)3, 5×10 -5 0.03 mol of tri-tert-butylphosphine and 0.03 mol of sodium tert-butoxide were heated to 105 °C and refluxed for 20 hours. A TLC sample was taken, showing no remaining amine compounds, indicating complete reaction. The mixture was allowed to cool naturally to room temperature, filtered, and the filtrate was rotary evaporated until no fraction remained. The filtrate was then passed through a neutral silica gel column to give compound 23. Elemental analysis and structure (molecular formula C) are required. 65 H 63 Theoretical values: C, 90.97; H, 7.40; N, 1.63. Measured values: C, 90.95; H, 7.45; N, 1.75. LC-MS: Measured value: 858.45 ([M+H]). + ).

[0169] Compound 187 was prepared using a method similar to that in Example 4, and the reactants involved are shown in Table 4 below:

[0170] Table 4

[0171]

[0172]

[0173] Example 6: Synthesis of Compound 433

[0174] Step (1)

[0175] Step (2)

[0176] (1) Under a nitrogen atmosphere, 0.06 mol of intermediate F-3 was added to a three-necked flask and dissolved in a mixed solvent (300 ml toluene, 90 ml H2O). The mixture was stirred under nitrogen for 1 hour, and then 0.05 mol of starting material C-3, 0.1 mol of K2CO3, and 0.005 mol of Pd(PPh3)4 were slowly added. The mixture was heated to 90 °C and reacted for 10 hours. The reaction was observed using thin-layer chromatography (TLC) until complete. After naturally cooling to room temperature, water was added to the reaction system for extraction. The mixture was separated, and the organic phase was rotary evaporated under reduced pressure until no fraction was obtained. The obtained substance was purified by silica gel column chromatography to obtain intermediate G-16.

[0177] (2) In a three-necked flask, under nitrogen protection, add 0.01 mol of intermediate G-16, 0.012 mol of raw material H-9, and 150 ml of toluene and stir to mix. Then add 5 × 10⁻⁶ ml of toluene. -5 mol Pd2(dba) 3 5×10 -5 0.03 mol of tri-tert-butylphosphine and 0.03 mol of sodium tert-butoxide were heated to 105 °C and refluxed for 21 hours. A TLC sample was taken, showing no remaining amine compounds, indicating complete reaction. The mixture was allowed to cool naturally to room temperature, filtered, and the filtrate was rotary evaporated until no fraction remained. The filtrate was then passed through a neutral silica gel column to give compound 433. Elemental analysis of the structure (molecular formula C) is required. 63 H 52 N2): Theoretical values: C, 90.39; H, 6.26; N, 3.35. Measured values: C, 90.45; H, 6.25; N, 3.55. LC-MS: Measured value: 837.45 ([M+H]) + ).

[0178] Compound 442 was prepared using a method similar to that in Example 6, and the reactants involved are shown in Table 5 below:

[0179] Table 5

[0180]

[0181] Fabrication of organic electroluminescent devices

[0182] The molecular structures of the materials involved in the following preparation process are shown below:

[0183]

[0184] Device Comparison Example 1

[0185] Organic electroluminescent devices are prepared according to the following steps:

[0186] like Figure 1 As shown, substrate layer 1 is transparent glass. Anode layer 2 (Ag (100nm)) is washed sequentially with alkaline washing, pure water washing, drying, and then ultraviolet-ozone washing to remove organic residues from the surface of the anode layer. After the above washing, a hole injection layer 3 (HT-1 and P-1 with a mass ratio of 97:3) is deposited on anode layer 2 using a vacuum evaporation apparatus. Next, a hole transport layer 4 (HT-1 with a thickness of 117nm) is deposited. Then, an electron blocking layer 5 (EB-1 with a thickness of 10nm) is deposited. After the electron blocking material deposition, the light-emitting layer 6 of the OLED light-emitting device is fabricated. Its structure includes BH-1 as the host material and BD-1 as the dopant material, with a doping ratio of 3% by weight, and a light-emitting layer thickness of 20nm. After the light-emitting layer 6, HB-1 is deposited to a thickness of 8nm as the hole blocking layer 7. On top of the hole-blocking layer 7, ET-1 and Liq are further deposited by vacuum evaporation, with an ET-1 to Liq mass ratio of 1:1. The vacuum-deposited film thickness of this material is 30 nm, and this layer serves as the electron transport layer 8. On the electron transport layer 8, a LiF layer with a thickness of 1 nm is formed by vacuum evaporation, and this layer serves as the electron injection layer 9. On the electron injection layer 9, a Mg:Ag electrode layer with a thickness of 16 nm is formed by vacuum evaporation, with a Mg to Ag mass ratio of 1:9, and this layer serves as the cathode layer 10. On the cathode layer 10, a 65 nm layer of CP-1 is vacuum-deposited as the CPL layer 11.

[0187] Device Comparison Example 2-3

[0188] The method was carried out according to the device comparison example 1, except that the organic materials in the hole injection layer and the hole transport layer were replaced with the organic materials shown in Table 3.

[0189] Device Examples 1-18

[0190] The method was carried out according to the device comparison example 1, except that the organic materials in the hole injection layer and hole transport layer were replaced with the organic materials shown in Table 6.

[0191] Table 6

[0192]

[0193]

[0194] Taking Example 1 as an example in the table above, "P-1:1=3:9710nm" in the second column indicates that the material used for the hole injection layer is Compound 1 and P-type dopant P-1, 3:97 refers to the weight ratio of P-type dopant to Compound 1 being 3:97, and 10nm represents the thickness of the layer; "1117nm" in the third column indicates that the material used is Compound 1, and the thickness of the layer is 117nm. The meanings in the other tables can be deduced similarly.

[0195] After fabricating the OLED light-emitting device as described above, the cathode and anode were connected using a known driving circuit, and various performance parameters of the device were measured. The performance measurement results of the devices in Examples 1-18 and Comparative Examples 1-3 are shown in Table 7.

[0196] Table 7

[0197]

[0198] Note: Current efficiency and color coordinates were measured using an IVL (current-voltage-luminance) testing system (Suzhou Fushida Scientific Instruments Co., Ltd.), with a current density of 10 mA / cm² during testing. 2 The lifetime testing system is the EAS-62C OLED device lifetime tester from System Technology Inc. of Japan. LT95 refers to the time it takes for the device brightness to decay to 95% at a specific brightness level. The high-temperature lifetime test temperature is 85℃, and LT80 refers to the time it takes for the device brightness to decay to 80% at a specific brightness level.

[0199] As can be seen from the results in Table 7, using the aromatic amine organic compounds of the present invention as hole injection and hole transport layer materials effectively improves device efficiency and device lifetime due to their high carrier transport rate, especially effectively improving the high-temperature lifetime of the device.

Claims

1. An aromatic amine organic compound, characterized in that, The structure of the organic compound is shown in general formula (1): General formula (1) In general formula (1), R1-R2 are each independently represented as hydrogen atoms; Ar1-Ar2 are independently represented as single bonds and phenylene, respectively; The L1-L4 are independently represented as single bond, phenylene, and naphthylene, respectively; R3-R6 are each independently represented as one of substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dimethylfluorenyl, or 1,1,4,4-tetramethyl-1,2,3,4-tetrahydronaphthalene. The n and m are independently represented as the numbers 0 or 1, and m + n ≥ 1; The substituents of the above-mentioned substituted or replaced groups may be selected from methyl, ethyl, tert-butyl or phenyl.

2. The aromatic amine organic compound according to claim 1, characterized in that, The structure of the organic compound is shown in any one of general formulas (1-1) to (1-2): General formula (1-1) General formula (1-2) In general formulas (1-1) to (1-2), the meanings of R1-R2, Ar1-Ar2, and R3-R6 are the same as those defined in claim 1; The m represents the number 1.

3. The aromatic amine organic compound according to claim 1, characterized in that, The structure of the organic compound is shown in any one of general formulas (1-3) or (1-6); General formula (1-3) General formula (1-6) In formulas (1-3) to (1-6), the meanings of Ar1-Ar2 and R3-R6 are the same as those defined in claim 1.

4. The aromatic amine organic compound according to claim 1, characterized in that, The structure of the organic compound is shown in any one of general formulas (1-7) to (1-11): General formula (1-7) General formula (1-8) General formula (1-9) General formula (1-10) General formula (1-11) In formulas (1-7) to (1-11), the meanings of Ar1-Ar2 and R3-R6 are the same as those defined in claim 1.

5. The aromatic amine organic compound according to claim 1, characterized in that, The meanings of R1-R2, Ar1-Ar2, and L1-L4 are the same as those defined in claim 1; R3 and R5 represent one of the following: substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dimethylfluorenyl, and 1,1,4,4-tetramethyl-1,2,3,4-tetrahydronaphthalene. R4 and R6 are each independently represented as one of substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, or substituted or unsubstituted diphenyl. The substituents of the above-mentioned substituted or substituted groups may be selected from deuterium, methyl, ethyl, tert-butyl or phenyl.

6. The aromatic amine organic compound according to claim 1, characterized in that, Ar1 and Ar2 are each independently represented as single bonds or as shown in the following structure: , or Any one of them; L1, L2, L3, and L4 are each independently represented as a single bond or as shown in the following structure: , , or Any one of them; R3-R6 are each independently represented as shown in the following structure: , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , or Any one of them.

7. The aromatic amine organic compound according to claim 1, characterized in that, The organic compound has a specific structure that is any one of the following: (1) (2) (3) (4) (5) (6) (7) (8) (9) (10) (11) (12) (13) (14) (15) (16) (17) (18) (19) (20) (21) (22) (23) (24) (25) (26) (30) (31) (32) (33) (34) (35) (36) (37) (39) (40) (41) (42) (43) (44) (45) (46) (47) (49) (50) (51) (52) (55) (57) (58) (59) (60) (61) (62) (63) (64) (65) (66) (67) (68) (69) (70) (71) (72) (73) (74) (75) (76) (80) (81) (82) (83) (84) (85) (86) (87) (88) (89) (90) (91) (92) (93) (94) (95) (96) (97) (98) (99) (100) (104) (105) (106) (107) (108) (109) (110) (111) (113) (114) (115) (116) (117) (118) (119) (120) (121) (122) (123) (124) (125) (126) (127) (128) (129) (130) (132) (134) (135) (136) (137) (138) (139) (140) (141) (142) (143) (144) (145) (146) (147) (148) (149) (153) (154) (155) (159) (160) (161) (162) (164) (165) (168) (169) (170) (171) (172) (173) (174) (175) (176) (177) (178) (179) (180) (181) (182) (183) (187) (188) (189) (190) (191) (192) (193) (194) (195) (198) (199) (200) (203) (204) (208) (209) (210) (211) (212) (213) (214) (215) (216) (217) (221) (222) (223) (224) (225) (226) (227) (228) (229) (231) (236) (240) (241) (242) (243) (244) (245) (246) (247) (248) (249) (250) (251) (252) (253) (257) (261) (262) (263) (264) (265) (266) (267) (268) (269) (270) (271) (272) (273) (274) (275) (278) (279) (280) (281) (282) (283) (285) (286) (287) (288) (289) (290) (291) (292) (293) (294) (295) (296) (297) (298) (299) (300) (301) (302) (303) (304) (305) (306) (307) (308) (309) (310) (311) (312) (313) (314) (315) (316) (317) (318) (319) (320) (321) (322) (323) (324) (325) (326) (327) (328) (329) (330) (331) (332) (333) (334) (335) (336) (337) (338) (339) (340) (341) (342) (343) (344) (345) (346) (347) (349) (350) (351) (352) (353) (354) (355) (356) (357) (358) (359) (360) (361) (362) (363) (364) (365) (366) (367) (368) (369) (370) (371) (377) (378) (379) (380) (381) (382) (383) (384) (385) (387) (388) (389) (390) (391) (392) (393) (394) (396) (397) (398) (399) (400) (401) (402) (403) (404) (405) (406) (407) (408) (410) (412) (416) (417) (432) (433) (434) (435) (436) (437) (438) (439) (442) (443) (444) (445) (446) (447) (448) (450) (458) (461) (462) (463) (466) (467) (452)。 8. An organic electroluminescent device, comprising, in sequence, an anode, an organic functional layer, and a cathode, characterized in that, The organic functional layer comprises any one of the aromatic amine organic compounds according to claims 1-7.

9. An organic electroluminescent device, comprising, in sequence, an anode, a hole transport region, a light-emitting region, an electron transport region, and a cathode, characterized in that, The hole transport region comprises any one of the aromatic amine organic compounds according to claims 1-7.

10. The organic electroluminescent device according to claim 9, characterized in that, The hole transport region includes a hole injection layer, a hole transport layer, and an electron blocking layer, wherein the hole transport layer comprises an aromatic amine organic compound as described in any one of claims 1-7.

11. The organic electroluminescent device according to claim 10, characterized in that, The hole injection layer and the hole transport layer comprise any one of the aromatic amine organic compounds according to claims 1-7.

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