Amine organic compound and organic electroluminescent device containing same

Abstract

The invention discloses an amine organic compound and an organic electroluminescent device containing the same, and belongs to the technical field of organic electroluminescent materials, the structure of the amine organic compound is shown as a general formula (1): # imgabs0 #, and the amine organic compound has excellent hole mobility and exciton blocking capability under high current density; when the amine organic compound is used for forming a light-emitting auxiliary layer material of the organic electroluminescent device, the effects of improving the efficiency of the device and prolonging the service life of the device are shown.

Description

Technical Field

[0001] The present invention relates to the technical field of organic electroluminescent materials, and particularly to an amine-based organic compound and an organic electroluminescent device comprising the same. Background Art

[0002] Organic Light Emission Diodes (OLED) can be used to manufacture new display products or new lighting products, and are expected to replace existing liquid crystal displays and fluorescent lighting, with a very broad application prospect. An organic electroluminescent device has a sandwich-like structure, including electrode material layers, and organic functional materials sandwiched between different electrode material layers. Various different organic functional materials are stacked together according to their uses to jointly form an organic electroluminescent device. As a current device, when a voltage is applied to the two electrodes of the organic electroluminescent device, positive and negative charges in the organic layer functional material layer act through an electric field, and the positive and negative charges further recombine in the light-emitting layer, thereby generating organic electroluminescence.

[0003] Currently, organic electroluminescent display technology has been applied in the fields of smartphones, tablet computers, televisions, etc. However, compared with the actual product application requirements, the performance of organic electroluminescent devices, such as luminous efficiency and service life, still needs to be further improved. Research on improving the performance of organic electroluminescent devices includes: reducing the driving voltage of the device, increasing the luminous efficiency of the device, and increasing the service life of the device. In order to continuously improve the performance of organic electroluminescent devices, not only innovation in the structure and manufacturing process of organic electroluminescent devices is required, but also continuous research and innovation on organic functional materials to create higher-performance organic functional materials.

[0004] Blue organic electroluminescent devices have always been the weak link in the development of full-color OLEDs. So far, it has been difficult to comprehensively improve the performance such as efficiency and life of blue light devices. Therefore, how to improve the performance of blue light devices remains a crucial issue and challenge in this field. Most of the blue light host materials used in the market are electron-deficient hosts. At low current densities, due to the preferential injection of holes, the pressure on the hole transport side is alleviated to a certain extent. As the current density increases, the amount of electron injection will increase more and more, resulting in the recombination region shifting towards the hole side, and the pressure on the hole side becoming greater and greater. In order to prevent excitons from transferring to the hole side, it is required that the light-emitting auxiliary layer material can effectively block excitons and efficiently transport holes to the light-emitting layer. Currently, most of the light-emitting auxiliary layer materials are traditional aromatic amine structures, and the electron tolerance of such structures in the prior art still cannot meet the requirements, and the hole mobility at high current densities still needs to be improved, so as to ensure the carrier balance in the light-emitting layer and prevent the device efficiency from decreasing and the life from shortening due to insufficient holes and the recombination region shifting towards the hole transport side. Summary of the Invention

[0005] In view of the above problems existing in the prior art, the present invention provides an amine organic compound and an organic electroluminescent device comprising the same. The amine organic compound of the present invention is used in the light-emitting auxiliary layer of the organic electroluminescent device, which can effectively improve the lifespan and efficiency of the organic electroluminescent device.

[0006] The technical solution provided by the present invention is as follows: an amine organic compound, the structure of the amine organic compound is shown as the general formula (1):

[0007]

[0008] In the general formula (1), Ar 2 represents the structure shown in formula (1) or formula (2);

[0009] Ar 1 represents a phenyl group substituted or unsubstituted by a substituent, a naphthyl group substituted or unsubstituted by a substituent, a biphenyl group substituted or unsubstituted by a substituent, a dibenzofuran group substituted or unsubstituted by a substituent, a dibenzothiophene group substituted or unsubstituted by a substituent, a phenanthrene group substituted or unsubstituted by a substituent, a triphenylene group substituted or unsubstituted by a substituent, a furyl group substituted or unsubstituted by a substituent, or a thiophene group substituted or unsubstituted by a substituent;

[0010] L 1 represents a single bond, a phenylene group substituted or unsubstituted by a substituent, a naphthylene group substituted or unsubstituted by a substituent, or a biphenylene group substituted or unsubstituted by a substituent;

[0011] L 2 represents a single bond or a phenylene group;

[0012] L 3 represents a phenylene group or a biphenylene group;

[0013] The substituent is selected from a deuterium atom, a phenyl group, a naphthyl group or a biphenyl group;

[0014] The substitution mode of the substituent is single-bond substitution or annelation substitution;

[0015] R 3 represents a phenyl group, a naphthyl group or a biphenyl group;

[0016] The X, X 1 , X 2 represent an oxygen atom or a sulfur atom;

[0017] (a)*, (b)*, (c)*, (d)*, (h)*, (i)*, (j)*, (m)*, (n)*, (p)* indicate the connection sites;

[0018] When Ar 2 is represented by formula (1), L 2 is represented by a single bond, and when L 3 is represented by a phenylene group, L 3 is not connected to (a)*;

[0019] When Ar 2 is represented by formula (1), the connecting site is (j)*, and when L 2 and L 3 are both phenylene groups, L 3 is not connected to (d)*;

[0020] When Ar 2 is represented by formula (2), the connecting site is (n)*, L 2 is represented by a single bond, and when L 3 is represented by a di(phenylene) group, X cannot be a sulfur atom.

[0021] Furthermore, any hydrogen atom in general formula (1) can be replaced by a deuterium atom.

[0022] Furthermore, the structure of the amine organic compound is as shown in any one of general formulas (1a) to (1b):

[0023]

[0024]

[0025] In general formulas (1a) to (1b), the meanings of X, L 1 , L 2 , L 3 , Ar 1 , Ar 2 , R 3 are the same as those defined in general formula (1) above.

[0026] Furthermore, the structure of the amine organic compound is as shown in any one of general formulas (A-1) to (A-13):

[0027]

[0028] In general formulas (A-1) to (A-13), the meanings of X, L 1 , L 2 , L 3 , Ar 1 , Ar 2 , R 3 are the same as those defined in general formula (1) above.

[0029] Preferably, the structure of the amine organic compound is as shown in any one of general formulas (B-1) to (B-18):

[0030]

[0031] In general formulas (B-1) to (B-18), the meanings of X, L 1 , L 2 , Ar 1 , Ar 2 , R 3 are the same as those defined in general formula (1) above.

[0032] Furthermore, the structure of the amine organic compound is as shown in any one of general formulas (C-1) to (C-2):

[0033]

[0034] In general formulas (C-1) to (C-2), the meanings of X, L 1 , L 2 , Ar 1 , Ar 2 , R 3 are the same as those defined in general formula (1) above;

[0035] k represents 1 or 2.

[0036] Furthermore, the structure of the amine organic compound is as shown in any one of general formulas (D-1) to (D-8):

[0037]

[0038] In general formulas (D-1) to (D-8), the meanings of X, L 1 , L 2 , Ar 1 , Ar 2 , R 3 are the same as those defined in general formula (1) above;

[0039] k represents 1 or 2.

[0040] Furthermore, the structure of the amine organic compound is as shown in general formulas (1-1) to (1-12):

[0041]

[0042]

[0043] In general formulas (1-1) to (1-12), the X, X 1 , X 2 , L1 、Ar 1 、R 3 have the same meanings as defined in the general formula (1) above. The positions indicated by (a)*, (b)*, (c)*, and (d)* represent the connection sites.

[0044] Further, the structure of the amine organic compound is as shown in any one of general formulas (2-1) to (2-14):

[0045]

[0046]

[0047] In general formulas (2-1) to (2-14), X, X 1 、X 2 、L 1 and Ar 1 have the same meanings as defined in the general formula (1) above;

[0048] Preferably, the structure of the amine organic compound is as shown in any one of general formulas (3-1) to (3-14):

[0049]

[0050]

[0051] In general formulas (3-1) to (3-14), L 1 and Ar 1 have the same meanings as defined in the general formula (1) above. Further, the structure of the amine organic compound is as shown in any one of general formulas (4-1) to (4-12):

[0052]

[0053]

[0054] In general formulas (4-1) to (4-12), L 1 and Ar 1 have the same meanings as defined in the general formula (1) above. Further, the structure of the amine organic compound is as shown in any one of general formulas (5-1) to (5-8):

[0055]

[0056] In general formulas (5-1) to (5-8), L 1 and Ar 1The meaning is the same as that defined in the general formula (1) above. Further, the structure of the amine organic compound is as shown in any one of general formulas (6-1) to (6-11):

[0057]

[0058]

[0059] In general formulas (6-1) to (6-11), the L 1 and Ar 1 have the same meaning as that defined in the general formula (1) above. Further, the L 1 is represented by a single bond or the following structure:

[0060] any one of them; the L 2 is represented by a single bond or the following structure:

[0061] any one of them;

[0062] The L 3 is represented by the following structure:

[0063] any one of them;

[0064] The Ar 1 is represented by the following structure:

[0065]

[0066] any one of them;

[0067] The Ar 2 is represented by the following structure:

[0068] any one of them;

[0069] * represents the connection site.

[0070] Further, any hydrogen atom in the amine organic compound can be replaced by a deuterium atom.

[0071] Further, the structure of the amine organic compound is selected from any one of the following structural formulas:

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102] The present invention also provides an organic electroluminescent device, which sequentially includes a substrate, a first electrode, an organic functional layer, and a second electrode, and the organic functional layer contains the amine organic compound.

[0103] Further, the organic functional layer includes a hole transport region, a light-emitting region, and an electron transport region, and the hole transport region contains the amine organic compound.

[0104] Further, the hole transport region includes a hole injection layer, a hole transport layer, and a light-emitting auxiliary layer, and the light-emitting auxiliary layer contains the amine organic compound.

[0105] Compared with the prior art, the beneficial technical effect of the present invention lies in:

[0106] The amine organic compound of the present invention has a combination of specific group types, has excellent exciton blocking ability and hole mobility at high current density, and is used in the light-emitting auxiliary layer of the organic electroluminescent device, thereby being beneficial to improving the device efficiency and device lifetime. Description of the Drawings

[0107] Figure 1 It is a schematic structural diagram of the organic electroluminescent device described in the embodiment;

[0108] In the figure, 1. Glass substrate layer; 2. Anode layer; 3. Hole injection layer; 4. Hole transport layer; 5. Light-emitting auxiliary layer; 6. Light-emitting layer; 7. Hole blocking layer; 8. Electron transport layer; 9. Electron injection layer; 10. Cathode layer; 11. CPL layer.

[0109] Figure 2 It is the 1H NMR spectrum of Compound 1 of the present invention. Detailed Embodiments

[0110] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the accompanying drawings in the embodiments of the present invention.

[0111] In the present invention, when a layer or element is referred to as being "on" another layer or substrate, the layer or element may be directly on the other layer or substrate, or an intermediate layer may also exist. In addition, it will also 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 one or more intermediate layers may also exist.

[0112] In the present invention, when describing electrodes, organic electroluminescent devices, and other structures, terms indicating orientation such as "upper", "lower", "top", and "bottom" only represent the orientation in a specific state, and do not mean that the relevant structures can only exist in the stated orientation; on the contrary, if the structure can be repositioned, for example, inverted, the orientation of the structure will change accordingly. Specifically, in the present invention, the "bottom" and "lower" sides of the electrode refer to the side of the electrode close to the substrate during the manufacturing process, and the opposite side away from the substrate is the "top" and "upper" sides.

[0113] In this specification, the term "substituted" 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 circumstances.

[0114] In this specification, the hole characteristic refers to the conductive characteristic that can supply electrons when an electric field is applied and is attributed to the highest occupied molecular orbital (HOMO) level. The holes formed in the anode are easily injected into the light-emitting layer and transported in the light-emitting layer.

[0115] In this specification, the electron characteristic refers to the conductive characteristic that can accept electrons when an electric field is applied and is attributed to the lowest unoccupied molecular orbital (LUMO) level. The electrons formed in the cathode are easily injected into the light-emitting layer and transported in the light-emitting layer.

[0116] The organic electroluminescent device of the present invention can be a bottom-emitting organic electroluminescent device, a top-emitting organic electroluminescent device, or a stacked organic electroluminescent device, and there is no specific limitation thereto.

[0117] The organic electroluminescent device of the present invention sequentially includes a substrate, a first electrode, an organic functional layer, and a second electrode. Among them, the organic functional layer includes a hole transport region, a light-emitting region, and an electron transport region. The hole transport region includes a hole injection layer, a hole transport layer, and a light-emitting auxiliary layer. The electron transport region includes a hole blocking layer, an electron transport layer, and an electron injection layer. In addition, a CPL layer can be provided on the second electrode.

[0118] The first electrode can be an anode or a cathode, and the second electrode can be a cathode or an anode.

[0119] In the organic electroluminescent device of the present invention, any substrate commonly used in organic electroluminescent devices can be used. Examples thereof 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 stabilities, transparencies, surface smoothness, and water resistances. Depending on the nature of the substrate, its usage direction is different. In the present invention, a transparent glass substrate is preferably used. The thickness of the substrate is not particularly limited.

[0120] Anode:

[0121] In the present invention, an anode can be formed on a substrate. The anode and the cathode face each other. The anode can be made of a conductor having a relatively high work function to assist hole injection, and can be, for example, a metal such as nickel, platinum, copper, zinc, silver, or an alloy thereof; a metal oxide such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); a combination of a metal and a 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-dioxythiophene)), and polyaniline, but not limited thereto. The thickness of the anode depends on the material used, and is generally 50 - 500 nm, preferably 70 - 300 nm, and more preferably 100 - 200 nm. In the present invention, metal Ag is preferably used.

[0122] Cathode:

[0123] The cathode can be made of a conductor having a relatively low work function to assist electron injection, and can be, for example, a metal or an alloy thereof such as magnesium, calcium, sodium, potassium, titanium, indium, aluminum, silver, tin, and combinations thereof; a multi-layer structure material such as LiF / Al, Li 2 O / Al, and BaF 2 / Ca, Mg / Ag, but not limited thereto. The thickness of the cathode depends on the material used, and is generally 10 - 50 nm, preferably 15 - 20 nm.

[0124] Light-emitting region:

[0125] In the present 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. As the host material and the guest material of the light-emitting region of the organic electroluminescent device of the present invention, the light-emitting layer materials known in the prior art for organic electroluminescent devices can be used.

[0126] In a preferred embodiment of the present invention, the light-emitting region contains one or two host material compounds.

[0127] In a preferred embodiment of the present invention, the host material used in the light-emitting region is selected from one or more of the following compounds BH1 - BH6:

[0128]

[0129] In the present invention, the light-emitting region may comprise a phosphorescent or fluorescent guest material to improve the fluorescence or phosphorescence characteristics of the organic electroluminescent device. Specific examples of the phosphorescent guest material include metal complexes such as iridium and platinum. For the fluorescent guest material, those commonly used in the art may be used. In a preferred embodiment of the present invention, the guest material of the light-emitting film layer used is selected from one of the following compounds BD1 to BD7:

[0130]

[0131] In the light-emitting region of the present invention, the ratio of the host material to the guest material used is 99:1 - 70:30, preferably 99:1 - 85:15 and more preferably 97:3 - 87:13, based on mass.

[0132] The thickness of the light-emitting region may be 10 - 50 nm, preferably 15 - 30 nm, but the thickness is not limited to this range.

[0133] Hole transport region:

[0134] In the organic electroluminescent device of the present invention, the hole transport region is disposed between the anode and the light-emitting region, and it includes a hole injection layer, a hole transport layer, and a light-emitting layer auxiliary layer.

[0135] Hole injection layer:

[0136] The hole injection material used in the hole injection layer (also referred to as the anode interface buffer layer) is a material that can sufficiently accept holes from the anode at a low voltage, 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 present invention, the hole injection layer is a mixed film layer of a host organic material and a P-type doping material. In order to enable holes to be smoothly injected from the anode into the organic film layer, the HOMO energy level of the host organic material and the P-type doping material must have certain characteristics, so as to expect the occurrence of a charge transfer state between the host material and the doping material, realize ohmic contact between the hole injection layer and the anode, and thus achieve efficient injection of holes from the electrode to the hole injection layer. This characteristic is summarized as: the difference between the HOMO energy level of the host material and the LUMO energy level of the P-type doping material ≤ 0.4 eV. Therefore, for hole-type host organic materials with different HOMO energy levels, different P-type doping materials need to be selected to match them in order to achieve ohmic contact at the interface and improve the hole injection effect.

[0137] Preferably, the host organic material is an aromatic amine organic compound, but is not limited thereto.

[0138] Preferably, the P-type doping material is a compound with charge conductivity selected from those disclosed in the prior art, and the P-type dopant can be selected from the compounds disclosed in the following patent documents: WO2011073149A, EP1968131A1, EP2276085A1, EP2213662A1, EP1722602A1, EP2045848A1, DE102007031220A1, US20100181555A1, US20100102709A1, WO2009003455A1, WO2010094378A1, WO2011120709A1, US20100096600A1, DE102012209523A1, CN101728485A, and WO2012095143A1, but not limited thereto.

[0139] In a preferred embodiment of the present invention, the P-type doping material used is selected from any one of the following compounds HI1 to HI8:

[0140]

[0141] In an embodiment of the present invention, the ratio of the host organic material to the P-type doping material is 99:1 - 95:5, preferably 99:1 - 97:3, by mass.

[0142] In a preferred embodiment of the present invention, the hole injection layer is a mixed film layer of an aromatic amine organic compound and a P-type doping material.

[0143] 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.

[0144] Hole transport layer:

[0145] In the organic electroluminescent device of the present invention, the hole transport layer can be disposed above the hole injection layer. The hole transport material is a suitable material with a high hole mobility, which can accept holes from the anode or the hole injection layer and transfer the holes into the light-emitting layer. Specific examples thereof include: aromatic amine organic materials, conductive polymers, block copolymers having both a conjugated part and a non-conjugated part, etc., but not limited thereto. In a preferred embodiment, the hole transport layer contains the same aromatic amine organic compound as the hole injection layer.

[0146] Preferably, as the hole transport layer material of the present invention, it can be arbitrarily selected from the compounds disclosed in the following prior art:

[0147]

[0148] The thickness of the hole transport layer of the present invention can be 80 - 200 nm, preferably 100 - 200 nm, more preferably 100 - 150 nm, but the thickness is not limited to this range.

[0149] Luminescent layer auxiliary layer:

[0150] In the organic electroluminescent device of the present invention, the luminescent layer auxiliary layer can be disposed between the hole transport layer and the luminescent layer, and in particular, it contacts the luminescent layer. The luminescent layer auxiliary layer is provided to contact the luminescent layer, and thus, the hole transfer at the interface between the luminescent layer and the hole transport layer can be precisely controlled. In one embodiment of the present invention, the luminescent layer auxiliary layer material is selected from the amine-based organic compounds represented by the general formula (1). The thickness of the luminescent layer auxiliary layer can be 5 - 20 nm, preferably 8 - 15 nm, but the thickness is not limited to this range.

[0151] Electron transport region:

[0152] In the organic electroluminescent device of the present invention, the electron transport region is disposed between the light-emitting region and the cathode, and it includes a hole blocking layer, an electron transport layer, and an electron injection layer, but is not limited thereto.

[0153] Electron injection layer:

[0154] The electron injection layer can be disposed between the electron transport layer and the cathode. The electron injection layer material is generally preferably a material having a low work function, such that electrons can be easily injected into the organic functional material layer. Preferably, the electron injection layer material is an N-type metal material. As the electron injection layer material of the organic electroluminescent device of the present invention, the electron injection layer materials known in the prior art for organic electroluminescent devices can be used, for example, lithium; lithium salts, such as lithium 8-hydroxyquinoline, lithium fluoride, lithium carbonate, or lithium azide; or cesium salts, cesium fluoride, cesium carbonate, or cesium azide.

[0155] The thickness of the electron injection layer of the present invention can 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.

[0156] Electron transport layer:

[0157] The electron transport layer can be disposed on the light-emitting film layer or (if present) the hole blocking layer. The electron transport layer material is a material that can easily receive electrons from the cathode and transfer the received electrons to the light-emitting layer. A material having a high electron mobility is preferred. As the electron transport layer of the organic electroluminescent device of the present invention, the electron transport layer materials known in the prior art for organic electroluminescent devices can be used.

[0158] As the electron transport layer of the organic electroluminescent device of the present invention, compounds disclosed in the following prior art can be used as the electron transport layer material for the organic electroluminescent device:

[0159]

[0160] The electron transport layer further includes other compounds conventionally used in the electron transport layer, for example, Alq 3 , Liq, preferably Liq.

[0161] 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.

[0162] Hole blocking layer

[0163] The hole blocking layer can be disposed between the light emitting layer and the electron transport layer. The hole blocking layer is to prevent the holes injected from the anode from passing through the light emitting layer and entering the electron transport layer. As the hole blocking layer of the organic electroluminescent device of the present invention, the following hole blocking layer materials disclosed in the prior art can be used:

[0164]

[0165]

[0166] Cover layer:

[0167] In order to improve the light extraction efficiency of the organic electroluminescent device, a CPL layer (i.e., a cover layer, also called a light extraction layer) can also be added on the cathode of the device. Compounds disclosed in the prior art in this field can be used as the CPL layer material:

[0168]

[0169] The thickness of the CPL cover layer is usually 5 - 300 nm, preferably 20 - 100 nm and more preferably 40 - 80 nm.

[0170] The organic electroluminescent device of the present invention may further include a packaging structure. The packaging structure can be a protective structure for preventing external substances such as moisture and oxygen from entering the organic layer of the organic electroluminescent device. The packaging structure can 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.

[0171] The method for preparing an organic electroluminescent device of the present invention includes successively laminating an anode, a hole injection layer, a hole transport layer, a light-emitting layer auxiliary layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a cathode, and optionally a cover layer on 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 the present invention, vacuum evaporation is preferably used to form each of the layers. Those skilled in the art can conventionally select various process conditions in the vacuum evaporation method according to actual needs.

[0172] In addition, it should be noted that the materials used to form each layer in the present invention can be formed into a film alone and used as a single layer, or can be formed into a film after being mixed with other materials and used as a single layer, and can also be a stacked structure between layers formed into a film alone, a stacked structure between layers formed into a film after being mixed, or a stacked structure between a layer formed into a film alone and a layer formed into a film after being mixed.

[0173] Preparation Examples

[0174] Preparation of Intermediate R-1:

[0175]

[0176] Under a nitrogen atmosphere, 60 mmol (17.86 g) of raw material E-1 was added to a three-necked flask, and a mixed solvent (100 ml of toluene, 50 ml of ethanol, 50 ml of H 2 O) was added to dissolve it. Nitrogen was passed through and stirred for 1.5 hours, then 50 mmol (10.20 g) of raw material D-1, 72 mmol (9.95 g) of K 2 CO 3 , and 2 mmol (2.31 g) of Pd(PPh 3 ) 4 were slowly added. The mixture was heated to 75 °C and reacted for 6 hours. The reaction was observed by thin layer chromatography (TLC) until the reaction was complete. It was naturally cooled, filtered, the filtrate was rotary evaporated, and passed through a silica gel column to obtain Intermediate R-1.

[0177] Preparation of Intermediate M-1:

[0178] (1)

[0179] (2)

[0180] (1) Add 50 mmol (13.94 g) of raw material A-1, 52.5 mmol (13.33 g) of raw material B-1, 200 ml of xylene, 0.5 mmol (0.112 g) of palladium acetate, 0.5 mmol (0.238 g) of 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl, and 60 mmol (4.92 g) of anhydrous NaOAc into a flask equipped with a magnetic stir bar. Transfer the resulting mixture to a preheated oil bath (110 °C) and stir for 17 hours. Evacuate the reaction mixture until all volatiles are distilled off, then distill the product into a liquid nitrogen trap to obtain intermediate P-1.

[0181] (2) Under a nitrogen atmosphere, add 60 mmol (16.97 g) of raw material C-1 to a three-necked flask, dissolve it with a mixed solvent (100 ml of toluene, 50 ml of ethanol, 50 ml of H 2 O), stir it under nitrogen for 1 hour, then slowly add 50 mmol (18.51 g) of intermediate P-1, 72 mmol (9.95 g) of K 2 CO 3 , 2 mmol (2.31 g) of Pd(PPh 3 ) 4 , heat to 75 °C, react for 4 hours, and monitor the reaction by thin-layer chromatography (TLC) until the reaction is complete. Cool naturally, filter, rotary evaporate the filtrate, and pass it through a silica gel column to obtain intermediate M-1.

[0182] Prepare the following intermediates M in the same manner as intermediate M-1, and the synthesis raw materials are shown in Table 1 below;

[0183] Table 1

[0184]

[0185]

[0186] Preparation of intermediate Q-1:

[0187]

[0188] In a three-necked flask, under nitrogen protection, add 10 mmol (3.99 g) of raw material H-1, 12 mmol (2.03 g) of raw material K-1, stir and mix with 150 ml of toluene, then add 4×10 -2 mmol (0.037 g) of Pd 2 (dba) 3 , 4×10 -2mmol (0.008g) tri-tert-butyl phosphine, 25mmol (2.40g) sodium tert-butoxide, heat to reflux for 14 hours, take a sample, and it shows that there is no raw material H-1 left, and the reaction is complete; cool naturally to room temperature, filter, and evaporate the filtrate until there is no fraction, and pass it through a silica gel column to obtain the intermediate Q-1.

[0189] The following intermediate Q was prepared in the same manner as intermediate Q-1, and the synthetic raw materials are shown in Table 2 below;

[0190] Table 2

[0191]

[0192]

[0193]

[0194]

[0195] Example 1: Synthesis of Compound 1

[0196]

[0197] In a three-necked flask, under nitrogen protection, 10 mmol (4.88 g) of intermediate Q-1, 12 mmol (3.03 g) of raw material A-9, and 150 ml of toluene were added and stirred, and then 5×10 -2 mmol(0.046g)Pd 2 (dba) 3 , 5×10 -2 mmol (0.010g) tri-tert-butylphosphine, 30mmol (2.88g) sodium tert-butoxide, heated to reflux for 14 hours, sampled the plate, showed no intermediate Q-1 remaining, the reaction was complete; cooled to room temperature naturally, filtered, the filtrate was evaporated until there was no fraction, and passed through a silica gel column to obtain compound 1. Elemental analysis structure (molecular formula C 52 H 33 NO 2 ): Elemental analysis test value: C, 88.70; H, 4.75; N, 1.94. LC-MS: Measured value: 704.31 ([M+H] + ).

[0198] The following compounds were prepared in the same manner as in Example 1, and the synthetic raw materials are shown in Table 3 below;

[0199] Table 3

[0200]

[0201]

[0202]

[0203]

[0204]

[0205] The application effects of the synthesized organic functional materials of the present invention in devices are described in detail below through Device Examples 1-30 and Device Comparative Examples 1-19. The manufacturing processes of the devices in Device Examples 1-30 and Device Comparative Examples 1-19 of the present invention are exactly the same, and the same substrate materials and electrode materials are used. The film thickness of the electrode materials is also kept consistent. The difference is that the light-emitting auxiliary layer materials in the devices are replaced.

[0206] Device Comparative Example 1

[0207] The specific preparation process is as follows:

[0208] As Figure 1 shown, on the glass substrate layer 1 is an anode layer 2 (Ag (100 nm)) formed by vacuum evaporation. On the anode layer 2, using a vacuum evaporation device, HT1 and HI1 with a film thickness of 10 nm are evaporated as the hole injection layer 3, and the mass ratio of HT1 and HI1 is 97:3. Then, HT1 with a thickness of 120 nm is evaporated as the hole transport layer 4. Subsequently, EB-1 with a thickness of 10 nm is evaporated as the light-emitting auxiliary layer 5. After the evaporation of the above light-emitting auxiliary material is completed, the light-emitting layer 6 of the organic electroluminescent device is fabricated. Its structure includes BH1 used as the host material and BD1 as the doping material in the light-emitting layer 6, and the doping ratio of the doping material is 3% by weight, and the film thickness of the light-emitting layer is 20 nm. After the above light-emitting layer 6, HB1 is continuously evaporated with a film thickness of 5 nm as the hole blocking layer 7. On the above hole blocking layer 7, ET-1 and Liq are continuously evaporated, and the mass ratio of ET-1 and Liq is 1:1. The vacuum evaporation film thickness of this material is 30 nm, and this layer is the electron transport layer 8. On the electron transport layer 8, a LiF layer with a film thickness of 1 nm is fabricated through a vacuum evaporation device, and this layer is the electron injection layer 9. On the electron injection layer 9, a Mg:Ag electrode layer with a film thickness of 16 nm, where the mass ratio of Mg and Ag is 1:9, is fabricated through a vacuum evaporation device, and this layer is used as the cathode layer 10. On the cathode layer 10, 65 nm of CP-1 is vacuum evaporated as the CPL layer 11.

[0209] The preparation methods of Device Examples 1-30 are the same as those of Device Comparative Example 1, except that the organic material of the light-emitting auxiliary layer uses the organic compound of the present invention application. The preparation methods of Device Comparative Examples 2-19 are the same as those of Device Comparative Example 1, except that the organic materials of the light-emitting auxiliary layer use comparative compounds EB-2, EB-3, EB-4, EB-5, EB-6, EB-7, EB-8, EB-9, EB-10, EB-11, EB-12, EB-13, EB-14, EB-15, EB-16, EB-17, EB-18 and EB-19. The specific structures of Device Examples 1-30 and Device Comparative Examples 2-19 are shown in Table 4. The molecular structural formulas of the related materials are as follows:

[0210]

[0211]

[0212] Table 4

[0213]

[0214]

[0215]

[0216]

[0217] Taking the row of Example 1 in Table 4 above as an example, "HI1:HT1 = 3:97 10nm" in the second column of the table means that the materials used for the hole injection layer are compound HT1 and P-type doping material HI1. 3:97 refers to the weight ratio of P-type doping material HI1 to compound HT1 being 3:97, and 10nm represents the thickness of this layer; "110nm" in the fourth column of the table means that the material used is compound 1 and the thickness of this layer is 10nm, and so on for the meanings in other tables.

[0218] After preparing the organic electroluminescent device as described above, the cathode and anode are connected by a known driving circuit, and various performances of the device are measured. The measured performance results of the devices of Examples 1-30 and Comparative Examples 1-19 are shown in Table 5.

[0219] Table 5

[0220]

[0221]

[0222] Note: LT95 refers to when the current density is 30 mA / cm 2The time when the device brightness decays to 95% of the original brightness; the current efficiency and color coordinates were measured using an IVL (current-voltage-brightness) test system (Suzhou FushiDa Scientific Instruments Co., Ltd.), and the current density was 10 mA / cm 2 ; the life test system is the EAS-62C type OLED life test system of System Science Co., Ltd. of Japan.

[0223] It can be seen from the device data results in Table 5 that compared with the device comparative examples 1-19, the organic electroluminescent device of the present invention has a greater improvement in both efficiency and life compared to the organic electroluminescent device of the known material.

[0224] The technical features of the above-described embodiments can be combined arbitrarily. For the sake of brevity of description, all possible combinations of the technical features in the above-described embodiments are not exhausted. However, as long as there is no contradiction in the combination of these technical features, it should be considered to be within the scope described in this specification.

[0225] For those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can still be made, and these all belong to the protection scope of the present invention. The protection scope of the present invention is subject to the appended claims.

Claims

1. An amine organic compound, characterized in that: The structure of the amine organic compound is shown in general formula (1): In the general formula (1), Ar2 represents a structure represented by formula (1) or formula (2); Ar1 represents phenyl which may be substituted by a substituent, naphthyl which may be substituted by a substituent, biphenyl which may be substituted by a substituent, dibenzofuranyl which may be substituted by a substituent, dibenzothiophenyl which may be substituted by a substituent, phenanthryl which may be substituted by a substituent, triphenylene which may be substituted by a substituent, furyl which may be substituted by a substituent, or thienyl which may be substituted by a substituent; L1 represents a single bond, a phenylene group substituted or unsubstituted by a substituent, a naphthylene group substituted or unsubstituted by a substituent, or a biphenylene group substituted or unsubstituted by a substituent; L2 represents a single bond or a phenylene group; L3 represents phenylene or biphenylene; The substituent is selected from a deuterium atom, a phenyl group, a naphthyl group or a biphenyl group; The substitution mode of the substituent is single bond substitution or ring substitution; R3 represents phenyl, naphthyl or biphenyl; Said X, X1, X2 represent oxygen atoms or sulfur atoms; The positions shown in (a)*, (b)*, (c)*, (d)*, (h)*, (i)*, (j)*, (m)*, (n)*, and (p)* indicate the connection sites; When Ar2 is represented by formula (1), L2 is represented by a single bond, and L3 is represented by a phenylene group, L3 is not connected to (a)*; When Ar2 is represented by formula (1), the connection site is (j)*, and L2 and L3 are both phenylene groups, L3 is not connected to (d)*; When Ar2 is represented by formula (2), the bonding site is (n)*, L2 is represented by a single bond, and L3 is represented by a biphenylene group, X cannot be a sulfur atom.

2. The amine organic compound according to claim 1, characterized in that: The structure of the amine organic compound is shown in any one of the general formulas (A-1) to (A-13): In general formula (A-1) to general formula (A-13), the meanings of X, L1, L2, L3, Ar1, Ar2, and R3 are the same as those defined in general formula (1) of claim 1; Preferably, the structure of the amine organic compound is as shown in any one of the general formulas (B-1) to (B-18): In general formulae (B-1) to (B-18), the meanings of X, L1, L2, Ar1, Ar2, and R3 are the same as those defined in general formula (1) of claim 1.

3. The amine organic compound according to claim 1, characterized in that: The structures of the amine organic compounds are shown in general formulas (1-1) to (1-12): In general formulas (1-1) to (1-12), the meanings of X, X1, X2, L1, Ar1, and R3 are the same as those defined in the general formula (1) of claim 1, and the positions indicated by (a)*, (b)*, (c)*, and (d)* represent connection sites.

4. The amine organic compound according to claim 1, characterized in that: The structure of the amine organic compound is shown in any one of the general formulas (2-1) to (2-14): In general formula (2-1) to general formula (2-14), the meanings of X, X1, X2, L1 and Ar1 are the same as those defined in general formula (1) of claim 1; Preferably, the structure of the amine organic compound is as shown in any one of the general formulas (3-1) to (3-14): In general formulae (3-1) to (3-14), L1 and Ar1 have the same meanings as defined in general formula (1) of claim 1.

5. The amine organic compound according to claim 1, characterized in that: The structure of the amine organic compound is shown in any one of the general formulas (4-1) to (4-12): In general formulae (4-1) to (4-12), the meanings of L1 and Ar1 are the same as those defined in general formula (1) of claim 1.

6. The amine organic compound according to claim 1, characterized in that: The structure of the amine organic compound is shown in any one of the general formulas (5-1) to (5-8): In general formulae (5-1) to (5-8), L1 and Ar1 have the same meanings as defined in general formula (1) of claim 1.

7. The amine organic compound according to claim 1, characterized in that: The structure of the amine organic compound is shown in any one of the general formulas (6-1) to (6-11): In general formulae (6-1) to (6-11), L1 and Ar1 have the same meanings as defined in general formula (1) of claim 1.

8. The amine organic compound according to any one of claims 1 to 7, characterized in that: The L1 represents a single bond or the following structure: Any of the following: The L2 is represented by a single bond or the following structure: Any of the following: The L3 is represented by the following structure: Any of the following: The Ar1 is represented by the following structure: Any of the following: The Ar2 is represented by the following structure: Any of the following: * indicates the attachment site.

9. The amine organic compound according to any one of claims 1 to 7, characterized in that: Any hydrogen atom in the amine organic compound may be substituted by a deuterium atom.

10. An amine organic compound according to claim 1, characterized in that: The structure of the amine organic compound is selected from any one of the following structural formulas:

11. An organic electroluminescent device, comprising a substrate, a first electrode, an organic functional layer and a second electrode in sequence, characterized in that: The organic functional layer contains the amine organic compound according to any one of claims 1 to 10; Preferably, the organic functional layer comprises a hole transport region, a light emitting region and an electron transport region, and the hole transport region contains the amine organic compound according to any one of claims 1 to 10.

12. The organic electroluminescent device according to claim 11, wherein the hole transport region comprises a hole injection layer, a hole transport layer and a light-emitting auxiliary layer, wherein: The light-emitting auxiliary layer contains the amine organic compound according to any one of claims 1 to 10.

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