Aromatic amine compound and organic electroluminescent device containing same

Abstract

The invention discloses an aromatic amine compound and an organic electroluminescent device containing the aromatic amine compound, and belongs to the technical field of organic electroluminescent materials, the structure of the aromatic amine compound is as shown in a general formula (1): # imgabs0 #, and the aromatic amine compound has excellent hole mobility under high current density; when the aromatic amine compound provided by the invention is used for forming a hole transport layer material of an 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 invention relates to the technical field of organic electroluminescent materials, in particular to an aromatic amine compound and an organic electroluminescent device containing the same. Background Art

[0002] Organic light-emitting diodes (OLEDs) can be used to manufacture new display products as well as new lighting products. They are expected to replace existing liquid crystal displays and fluorescent lighting, and have a wide range of applications. Organic light-emitting diodes are like sandwich structures, including electrode material films and organic functional materials sandwiched between different electrode material films. Various organic functional materials are superimposed on each other according to their uses to form organic light-emitting diodes. As a current device, when voltage is applied to the electrodes at both ends of the organic light-emitting diode, the positive and negative charges in the organic layer functional material film layer are further compounded in the light-emitting layer through the electric field, generating organic electroluminescence.

[0003] Currently, organic electroluminescent display technology has been applied in smart phones, tablet computers, televisions and other fields. However, compared with the actual product application requirements, the luminous efficiency and service life of organic electroluminescent devices need to be further improved. Research on improving the performance of organic electroluminescent devices includes: reducing the driving voltage of the device, improving the luminous efficiency of the device, and improving the service life of the device. In order to continuously improve the performance of organic electroluminescent devices, it is necessary not only to innovate the structure and manufacturing process of organic electroluminescent devices, but also to continuously study and innovate organic functional materials to create higher performance organic functional materials.

[0004] Blue organic electroluminescent devices have always been the weak point in the development of full-color OLEDs. So far, the efficiency and life of blue light devices have been difficult to be comprehensively improved. Therefore, how to improve the performance of blue light devices is still a crucial issue and challenge facing this field. At present, most of the blue light host materials used in the market are electron-biased hosts. Due to the preferential injection of holes at low current density, the pressure on the hole transport side is relieved to a certain extent. As the current density increases, the amount of electron injection will increase, causing the recombination area to shift to the hole side, and the pressure on the hole side will increase. In order to prevent the excitons from being transferred to the hole side, the hole transport layer material is required to effectively block the excitons and efficiently transfer the holes to the light-emitting layer. At present, most hole transport layer materials are traditional aromatic amine structures. The electronic tolerance of this type of structure in the prior art still cannot meet the demand. The hole mobility at high current density still needs to be improved, so as to ensure the carrier balance of the light-emitting layer and prevent the recombination area from shifting to the hole transport side due to insufficient holes, resulting in reduced device efficiency and shortened life. Summary of the invention

[0005] In view of the above problems existing in the prior art, the applicant of the present invention provides an aromatic amine organic compound and an organic electroluminescent device containing the same. The compound of the present invention has excellent hole transport ability and thermal stability. When the aromatic amine organic compound of the present invention is used to form a hole transport material of an organic electroluminescent device, the device efficiency (index) can be improved and the life can be extended at the same time.

[0006] The present invention provides the following technical solution: an aromatic amine compound, the structure of which is shown in the general formula (1):

[0007]

[0008] The L 1 -L 3 Each independently represents a direct bond, a substituted or unsubstituted C6-C30 arylene group, or a substituted or unsubstituted 5- to 30-membered heteroarylene group;

[0009] The R 1 , R 2 Each independently represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C6-C30 aryl group, or a substituted or unsubstituted 5- to 30-membered heteroaryl group;

[0010] The R 3 , R 4 , R 5 , R 6 The same or different ones are represented by a hydrogen atom, a deuterium atom, a C1-C10 alkyl group, a C3-C20 cycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, or a substituted or unsubstituted 5- to 30-membered heteroaryl group;

[0011] The R 3 and R 4 Between 4 and R 5 Between 5 and R 6 They can bond with each other to form a C6-C30 aliphatic ring;

[0012] The Ar 1 ,Ar 2 Each independently represents a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted 5- to 30-membered heteroaryl group, or a C3-C10 cycloalkyl group;

[0013] The substituent replacing the above substitutable group is selected from a deuterium atom, a C1-C10 alkyl group, a C1-C10 alkyl group substituted with a deuterium atom, a C6-C30 aryl group, a C6-C30 aryl group substituted with a deuterium atom, a 5- to 30-membered heteroaryl group, or a 5- to 30-membered heteroaryl group substituted with a deuterium atom;

[0014] The heteroatom in the heteroaryl group is selected from one or more of oxygen atoms, sulfur atoms and nitrogen atoms;

[0015] Any hydrogen atom in the general formula (1) may be substituted by a deuterium atom.

[0016] In a preferred embodiment, the structure of the aromatic amine compound is shown in the general formula (2-1):

[0017]

[0018] In the general formula (2-1), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , L 1 -L 3 ,Ar 1 ,Ar 2 has the same meaning as in the general formula (1).

[0019] In a preferred embodiment, the structure of the aromatic amine compound is as shown in the general formula (3-1) or the general formula (3-2):

[0020]

[0021] In the general formula (3-1) to the general formula (3-2), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , L 1 , L 2 ,Ar 1 ,Ar 2 has the same meaning as in the general formula (1).

[0022] In a preferred embodiment, the structure of the aromatic amine compound is selected from any one of the general formulas (4-1) to (4-6):

[0023]

[0024] In the general formula (4-1) to the general formula (4-6), the R 3 , R 4 , R5 , R 6 The same or different C1-C10 alkyl, C3-C20 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 5- to 30-membered heteroaryl;

[0025] The R 4 and R 5 They can bond with each other to form a C6-C10 aliphatic ring;

[0026] The L 1 , L 2 ,Ar 1 ,Ar 2 , R 1 , R 2 has the same meaning as in the general formula (1).

[0027] In a preferred embodiment, the structure of the aromatic amine compound is selected from any one of the general formulas (5-1) to (5-16):

[0028]

[0029]

[0030] In the general formula (5-1) to the general formula (5-16), the L 1 , L 2 ,Ar 1 ,Ar 2 has the same meaning as in the general formula (1).

[0031] Preferably, the L 1 , L 2 , L 3 Each independently represents a single bond, a substituted or substituted phenylene group, a substituted or unsubstituted naphthylene group, or a substituted or unsubstituted biphenylene group;

[0032] The Ar 1 ,Ar 2 each independently represents one of substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted furyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted thienyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted indenyl, substituted or unsubstituted piperonyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted spirofluorenyl, substituted or unsubstituted indolyl, 1,1,4,4-tetramethyl-1,2,3,4-tetrahydronaphthalene, and 1,4-benzodioxanyl;

[0033] The R 1 , R 2 , R 3 , R 4 , R 5 , R 6 Each independently represents one of a hydrogen atom, a deuterium atom, a methyl group, a deuterated methyl group, an ethyl group, a tert-butyl group, a phenyl group, an adamantyl group, a naphthyl group, and a biphenyl group;

[0034] The substituents replacing the above substitutable groups are selected from one or more of deuterium atoms, methyl, deuterated methyl, ethyl, tert-butyl, adamantyl, phenyl, naphthyl, biphenyl, dibenzofuranyl, carbazolyl, phenanthryl, dibenzothienyl, and benzofuranyl.

[0035] Preferably, the Ar 1 and Ar 2 Each of them is independently represented as follows:

[0036]

[0037]

[0038]

[0039] The L 1 , L 2 , L 3 Each independently represents a single bond or the following structure:

[0040] Any of the following;

[0041] * indicates the attachment site.

[0042] Preferably, the structure of the aromatic amine compound is selected from the following structures:

[0043]

[0044]

[0045]

[0046]

[0047]

[0048]

[0049]

[0050]

[0051]

[0052]

[0053]

[0054]

[0055] Any one of .

[0056] The second aspect of the present invention is to provide an organic electroluminescent device, comprising a substrate, a cathode, an anode and an organic functional layer, wherein the organic functional layer is located between the cathode and the anode, the substrate is adjacent to the cathode or the anode, and the organic functional layer comprises a hole transport region, a light emitting region and an electron transport region, wherein the hole transport region contains the aromatic amine compound described in the present invention.

[0057] In a preferred embodiment, the hole transport region includes a hole injection layer, a hole transport layer and a light-emitting auxiliary layer, and the hole injection layer and / or the hole transport layer contain the aromatic amine compound described in the present invention.

[0058] Compared with the prior art, the beneficial technical effects of the present invention are:

[0059] (1) The structure of the aromatic amine compounds of the present invention is relatively stable, so it is beneficial for the molecules to maintain a stable film phase during film formation, thereby ensuring the physical and chemical stability of the film phase and the stability of the film phase under point formation, which is beneficial to obtaining a long device life.

[0060] (2) Since the compound of the present invention has a stable structure, when hole injection becomes stronger at high current density, holes can still be conducted to the light-emitting layer through different carrier conduction channels, thereby ensuring the hole concentration at high current density and improving the luminescence efficiency of the device.

[0061] (3) Because the structural characteristics of the organic compound of the present invention are conducive to improving the glass transition temperature of the molecule, it is also conducive to reducing the evaporation temperature of the molecule. That is to say, even if the molecular weight of the structure is relatively high, it can ensure a lower evaporation temperature. This excellent performance is not only conducive to the thermal evaporation of the material, but also controls the thermal decomposition rate of the material, thereby improving the stability of the material in device applications.

[0062] (4) The compounds of the present invention have a relatively high hole mobility, so that the compounds of the present invention can be used as hole transport materials to effectively improve device efficiency and prolong device life. BRIEF DESCRIPTION OF THE DRAWINGS

[0063] Figure 1 is a schematic structural diagram of the organic electroluminescent device described in the embodiment;

[0064] In the figure, 1 is a transparent substrate layer; 2 is an anode layer; 3 is a hole injection layer; 4 is a hole transport layer; 5 is a light-emitting auxiliary layer; 6 is a light-emitting layer; 7 is a hole blocking layer; 8 is an electron transport layer; 9 is an electron injection layer; 10 is a cathode layer; 11 is a CPL layer. DETAILED DESCRIPTION

[0065] The technical solutions in the embodiments of the present invention will be described clearly and completely below in conjunction with the accompanying drawings in the embodiments of the present invention.

[0066] 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 intervening layers may also be present. In addition, 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 one or more intervening layers may also be present.

[0067] In the present invention, when describing electrodes and organic electroluminescent devices, as well as other structures, the words "upper", "lower", "top" and "bottom" used to indicate orientation only indicate the orientation in a certain state, and do not mean that the related structure can only exist in the orientation described; on the contrary, if the structure can change its position, such as inverted, the orientation of the structure will be changed accordingly. Specifically, in the present invention, the "bottom" or "lower" side of the electrode refers to the side of the electrode close to the substrate during the preparation process, and the opposite side away from the substrate is the "top" or "upper" side.

[0068] In this specification, the term "substituted" means that one or more hydrogen atoms on a designated atom or group are replaced by a designated group, provided that the normal valency of the designated atom is not exceeded under the existing circumstances.

[0069] In this specification, the hole characteristic refers to a characteristic that can donate electrons when an electric field is applied and holes formed in the anode are easily injected into the light-emitting layer and transported in the light-emitting layer due to the conductive characteristic according to the highest occupied molecular orbital (HOMO) level.

[0070] In this specification, the electronic characteristics refer to the characteristics that electrons formed in the cathode can be easily injected into the light-emitting layer and transported in the light-emitting layer due to the conductive characteristics according to the lowest unoccupied molecular orbital (LUMO) level when an electric field is applied.

[0071] The organic electroluminescent device of the present invention may be a bottom-emitting organic electroluminescent device, a top-emitting organic electroluminescent device, or a stacked organic electroluminescent device, without any particular limitation.

[0072] In the organic electroluminescent device of the present invention, any substrate commonly used in organic electroluminescent devices can be used. Examples thereof are transparent substrates, such as glass or transparent plastic substrates; opaque substrates, such as silicon substrates; flexible polyimide (PI) film substrates. Different substrates have different mechanical strengths, thermal stability, transparency, surface smoothness, and waterproofness. Depending on the properties of the substrate, its use direction is different. In the present invention, a transparent glass substrate is preferably used. The thickness of the substrate is not particularly limited.

[0073] anode:

[0074] In the present invention, an anode may be formed on a substrate. The anode and the cathode are opposite to each other. The anode may be made of a conductor having a higher work function to facilitate hole injection, and may 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-dioxy)thiophene) and polyaniline, but not limited thereto. The thickness of the anode depends on the material used, and is typically 50-500 nm, preferably 70-300 nm, and more preferably 100-200 nm. In the present invention, metal Ag is preferably used.

[0075] cathode:

[0076] The cathode can be made of a conductor with a lower work function to facilitate electron injection, such as a metal or its alloy, such as magnesium, calcium, sodium, potassium, titanium, indium, aluminum, silver, tin, and combinations thereof; a multilayer structure material, such as LiF / Al, Li 2 O / Al and BaF 2 / Ca, but not limited thereto. The thickness of the cathode depends on the material used, and is generally 10-50 nm, preferably 15-20 nm.

[0077] Emitting area:

[0078] In the present invention, the light-emitting region can be arranged 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 for organic electroluminescent devices known in the prior art can be used.

[0079] In a preferred embodiment of the present invention, the light emitting region comprises one or two host material compounds.

[0080] In a preferred embodiment of the present invention, the host material of the light-emitting region used is selected from one or more of the following compounds BH1-BH6:

[0081]

[0082] In the present invention, the light-emitting region may contain a phosphorescent or fluorescent guest material to improve the fluorescent or phosphorescent properties of the organic electroluminescent device. Specific examples of phosphorescent guest materials include metal complexes of iridium, platinum, etc. For fluorescent guest materials, those commonly used in the art can 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:

[0083]

[0084] 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.

[0085] 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.

[0086] Hole transport region:

[0087] In the organic electroluminescent device of the present invention, the hole transport region is arranged between the anode and the light emitting region, and includes a hole injection layer, a hole transport layer and a light emitting layer auxiliary layer.

[0088] Hole injection layer:

[0089] The hole injection material used in the hole injection layer (also called the anode interface buffer layer) is a material that can fully 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 main organic material and a P-type doping material. In order to smoothly inject holes from the anode into the organic film layer, the HOMO energy level of the main organic material must have certain characteristics with the P-type doping material, so that it is expected to realize the occurrence of charge transfer states between the main material and the doping material, and realize ohmic contact between the hole injection layer and the anode, thereby realizing efficient injection of holes from the electrode to the hole injection layer. This feature is summarized as: the difference between the HOMO energy level of the main organic material and the LUMO energy level of the P-type doping material is ≤0.4eV. Therefore, for hole-type main 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.

[0090] Preferably, the main organic material is the aromatic amine compound of the present invention.

[0091] Preferably, the P-type doping material is selected from the compounds with charge conductivity 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, DE102007031220A 1. US20100181555A1, US20100102709A1, WO2009003455A1, WO2010094378A1, WO2011120709A1, US20100096600A1, DE102012209523A1, CN101728485A and WO2012095143A1, but are not limited thereto.

[0092] 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:

[0093]

[0094] In one embodiment of the present invention, the ratio of the host organic material to the P-type doping material used is 99:1-95:5, preferably 99:1-97:3, based on mass.

[0095] In a preferred embodiment of the present invention, the hole injection layer is a mixed film layer of the aromatic amine compound of the present invention and a P-type doping material.

[0096] The thickness of the hole injection layer of the present invention may be 5-20 nm, preferably 8-15 nm, but the thickness is not limited to this range.

[0097] Hole transport layer:

[0098] In the organic electroluminescent device of the present invention, a hole transport layer may be disposed above the hole injection layer. The hole transport material is a suitable material having a high hole mobility, which can accept holes from the anode or the hole injection layer and transfer the holes to the light-emitting layer. In a preferred embodiment, the hole transport layer comprises an aromatic amine compound of the present invention represented by the general formula (1).

[0099] The thickness of the hole transport layer of the present invention may be 80, 100 or 200 nm, preferably 100-150 nm, but the thickness is not limited to this range.

[0100] Luminous layer auxiliary layer:

[0101] In the organic electroluminescent device of the present invention, the light-emitting layer auxiliary layer may be arranged between the hole transport layer and the light-emitting layer, and in particular contact the light-emitting layer. The light-emitting layer auxiliary layer is arranged to contact the light-emitting layer, and therefore, the hole transfer at the interface between the light-emitting layer and the hole transport layer can be accurately controlled. In one embodiment of the present invention, the light-emitting layer auxiliary layer material is selected from carbazole aromatic amine derivatives. The thickness of the light-emitting layer auxiliary layer may be 5-20nm, preferably 8-15nm, but the thickness is not limited to this range.

[0102] As the auxiliary layer material of the light-emitting layer of the present invention, it can be selected from the following compounds disclosed in the prior art:

[0103]

[0104] Electron transport region:

[0105] 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 a hole blocking layer, an electron transport layer and an electron injection layer, but is not limited thereto.

[0106] Electron injection layer:

[0107] The electron injection layer may 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 so that electrons are 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 material for organic electroluminescent devices known in the prior art can be used, for example, lithium; lithium salts such as 8-hydroxyquinoline lithium, lithium fluoride, lithium carbonate or lithium azide; or cesium salts, cesium fluoride, cesium carbonate or cesium azide.

[0108] 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.

[0109] Electron transport layer:

[0110] The electron transport layer may be disposed on the light-emitting film layer or (if present) the hole blocking layer. The electron transport layer material is a material that easily receives electrons from the cathode and transfers the received electrons to the light-emitting layer. 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 material for organic electroluminescent devices known in the prior art can be used.

[0111] As the electron transport layer of the organic electroluminescent device of the present invention, the following compounds disclosed in the prior art can be used as electron transport layer materials of the organic electroluminescent device:

[0112]

[0113]

[0114] The electron transport layer further includes other compounds conventionally used in electron transport layers, for example, Alq3, LiQ, preferably LiQ.

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

[0116] Hole blocking layer

[0117] The hole blocking layer may be disposed between the light-emitting layer and the electron transport layer. The hole blocking layer is used to block 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 hole blocking layer materials for organic electroluminescent devices disclosed in the following prior art may be used:

[0118]

[0119] Cover:

[0120] In order to improve the light extraction efficiency of the organic electroluminescent device, a light extraction layer (ie, CPL layer, also called covering layer) may be added on the cathode of the device. The compounds disclosed in the prior art may be used as the CPL layer material.

[0121]

[0122] The thickness of the CPL cover layer is typically 5-300 nm, preferably 20-100 nm and more preferably 40-80 nm.

[0123] The organic electroluminescent device of the present invention may further include an encapsulation structure. The encapsulation structure may be a protective structure that prevents foreign substances such as moisture and oxygen from entering the organic layer of the organic electroluminescent device. The encapsulation structure may be, for example, a can, such as a glass can or a metal can; or a thin film covering the entire surface of the organic layer.

[0124] The method for preparing an organic electroluminescent device of the present invention comprises laminating an anode, a hole injection layer, a hole transport layer, a light-emitting layer auxiliary layer, an organic film layer, an electron transport layer, an electron injection layer and a cathode successively on a substrate, and optionally a covering layer. In this regard, vacuum deposition, vacuum evaporation, spin coating, casting, LB method, inkjet printing, laser printing or LITI methods can be used, but are not limited thereto. In the present invention, it is preferred to use a vacuum evaporation method to form the various layers. Those skilled in the art can conventionally select various process conditions in the vacuum evaporation method according to actual needs.

[0125] In addition, it should be noted that the materials used to form each layer described in the present invention can be formed into a film alone and used as a single layer, or can be mixed with other materials to form a film and used as a single layer. It can also be a stacked structure between layers formed into films alone, a stacked structure between layers formed into films after mixing, or a stacked structure of layers formed into films alone and layers formed into films after mixing.

[0126] Preparation Example

[0127] Preparation of intermediate D:

[0128] Step (1)

[0129] Step (2)

[0130] (1) In a nitrogen atmosphere, 0.08 mol (24.56 g) of raw material A-1 was added to a three-necked flask, and a mixed solvent (300 ml of toluene, 90 ml of H 2 O) was dissolved, stirred for 1 hour under nitrogen, and then 0.07 mol (8.61 g) of raw material B-1, 0.1 mol (13.82 g) of K2 CO 3 、0.005mol(5.78g)Pd(PPh 3 ) 4 , heated to 90°C, reacted for 8 hours, and observed the reaction by thin layer chromatography (TLC) until the reaction was complete. Naturally cooled, filtered, and the filtrate was rotary evaporated and passed through a silica gel column to obtain intermediate C-1.

[0131] (2) Under nitrogen atmosphere, 0.01 mol (3.05 g) of intermediate C-1, 0.0079 mmol (0.0034 g) of Co(dmg(BF 2 )) 2 (OH 2 ) 2 and 16 mL of MeCN were added to a dry quartz test tube with a magnet. The quartz test tube was placed in a glove box, acetonitrile was added to the quartz tube in the glove box, and the mixture was irradiated with a 25W UV lamp at room temperature and stirred for 18 hours. After the reaction was completed, dichloromethane was used for extraction, and the solvent was removed under vacuum, and the residue was purified by column chromatography to obtain the desired intermediate D-1.

[0132] (3) Under nitrogen atmosphere, 0.07 mol (21.21 g) of intermediate D-1 was added to a three-necked flask, and a mixed solvent (300 ml toluene, 90 ml H 2 O) was dissolved, stirred for 1 hour under nitrogen, and then 0.09 mol (14.13 g) of raw material B-9, 0.09 mol (12.42 g) of K 2 CO 3 、0.004mol(4.62g)Pd(PPh 3 ) 4 , heated to 95°C, reacted for 12 hours, and observed the reaction by thin layer chromatography (TLC) until the reaction was complete. Naturally cooled, filtered, the filtrate was rotary evaporated, and passed through a silica gel column to obtain intermediate D-9.

[0133] The following intermediate D was prepared in the same manner as intermediate D-1, and the synthetic raw materials are shown in Table 1 below;

[0134] Table 1

[0135]

[0136]

[0137] Preparation of intermediate F:

[0138]

[0139] In a three-necked flask, under nitrogen protection, add 0.05 mol (13.25 g) of raw material G-1, 0.04 mol (6.81 g) of raw material E-1, 150 ml of toluene, stir and mix, then add 5×10 -5 mol(0.046g)Pd 2 (dba) 3 , 5×10 -5 mol (0.010g) tri-tert-butyl phosphine, 0.03mol (2.88g) sodium tert-butoxide, heated to 105°C, refluxed for 21 hours, sampling point plate, showing that there was no residue of raw material E-1, and the reaction was complete; naturally cooled to room temperature, filtered, and the filtrate was rotary evaporated until there was no fraction, and passed through a neutral silica gel column to obtain intermediate F-1.

[0140] The following intermediate F was prepared in the same manner as intermediate F-1, and the synthetic raw materials are shown in Table 2 below;

[0141] Table 2

[0142]

[0143]

[0144] Example 1: Synthesis of Compound 176

[0145]

[0146] In a three-necked flask, under nitrogen protection, add 0.06 mol (18.18 g) of intermediate D-1, 0.05 mol (19.91 g) of intermediate F-1, and 150 ml of toluene, stir and mix, then add 6×10 -5 mol(0.069g)Pd 2 (dba) 3 , 6×10 -5 mol (0.012g) tri-tert-butylphosphine, 0.04mol (3.84g) sodium tert-butoxide, heated to 106°C, refluxed for 24 hours, sampled the plate, showed no intermediate F-1 remained, the reaction was complete; cooled to room temperature naturally, filtered, the filtrate was evaporated until there was no fraction, passed through a neutral silica gel column, and compound 176 was obtained. Elemental analysis structure (molecular formula C 51 H 37 N): Elemental analysis test value: C, 92.25; H, 5.64; N, 2.09. LC-MS: Measured value: 664.28 ([M+H] + ).

[0147] The following compounds were prepared in the same manner as in Example 1, and the synthetic raw materials are shown in Table 3 below;

[0148] Table 3

[0149]

[0150]

[0151]

[0152]

[0153] The following describes in detail the application effect of the synthesized mechanical functional material of the present invention in the device through device examples 1-23 and device comparative examples 1-6. The device manufacturing process of device examples 1-23 of the present invention is exactly the same as that of device comparative examples 1-6, and the same substrate material and electrode material are used, and the film thickness of the electrode material is also consistent. The difference is that the hole injection layer and hole transport layer materials in the device are replaced.

[0154] Device Comparison Example 1

[0155] The specific preparation process is as follows:

[0156] like Figure 1 As shown, the glass substrate layer 1 is an anode layer 2 (Ag (100nm)) formed by vacuum evaporation. On the anode layer 2, a vacuum evaporation device is used to evaporate HT1 and HI1 with a film thickness of 10nm as a hole injection layer 3, and the mass ratio of HT1 and HI1 is 97:3. Then, HT-1 with a thickness of 120nm is evaporated as a hole transport layer 4. Then, EB-1 with a thickness of 10nm is evaporated as a light-emitting auxiliary layer 5. After the evaporation of the above-mentioned light-emitting auxiliary materials is completed, the light-emitting layer 6 of the OLED light-emitting device is prepared, and its structure includes BH1 used as the main material of the OLED light-emitting layer 6, BD1 as the doping material, the doping ratio of the doping material is 3% by weight, and the thickness of the light-emitting layer is 20nm. After the above-mentioned light-emitting layer 6, HB1 is continuously evaporated with a film thickness of 5nm as a hole blocking layer 7. On top of the above-mentioned 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-deposited film thickness of the 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 made by 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 is made by a vacuum evaporation device, and the mass ratio of Mg to Ag is 1:9, and this layer is used as the cathode layer 10. On the cathode layer 10, 65 nm of CP-1 is vacuum-deposited as the CPL layer 11.

[0157] The preparation method of device embodiments 1-23 is the same as that of device comparison example 1, except that the main organic material of the hole injection layer and the organic material of the hole transport layer use the organic compounds applied for in the present invention. The preparation method of device comparison examples 2-6 is the same as that of device comparison example 1, except that the main organic material of the hole injection layer and the organic material of the hole transport layer use comparative compounds HT-2, HT-3, HT-4, HT-5, and HT-6. The structures of device embodiments 1-23 and device comparison examples 2-6 are shown in Table 4 for details.

[0158] The molecular structure formula of the relevant materials is shown below:

[0159]

[0160]

[0161] Table 4

[0162]

[0163]

[0164]

[0165] Taking Comparative Example 1 as an example in Table 4 above, "HI1:HT-1=3:9710nm" in the second column indicates that the materials used for the hole injection layer are compound HT-1 and P-type dopant material HI1, 3:97 means that the weight ratio of P-type dopant material HI1 and compound HT-1 is 3:97, and 10nm indicates the thickness of the layer; "EB-110nm" in the fourth column indicates that the material used is EB-1 and the thickness of the layer is 10nm, and so on for the meanings in other tables.

[0166] After the organic electroluminescent device is prepared as described above, the cathode and the anode are connected by a known driving circuit, and various properties of the device are measured. The measured performance results of the devices of Examples 1-23 and Comparative Examples 1-6 are shown in Table 5.

[0167] Table 5

[0168]

[0169]

[0170] Note: LT95 refers to the current density of 30mA / cm 2 The time taken for the device brightness to decay to 95% of the original brightness under the condition of 100V. The current efficiency and color coordinates were tested using an IVL (current-voltage-luminance) test system (Suzhou Fushida Scientific Instrument Co., Ltd.) at a current density of 10 mA / cm 2The life test system is the EAS-62C OLED life test system produced by Japan System Research Co., Ltd.

[0171] It can be seen from the device data results in Table 5 that, compared with device comparison examples 1-6, the organic light-emitting device of the present invention has a significant improvement in both efficiency and lifespan relative to known materials.

[0172] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are exhaustively listed. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0173] For those skilled in the art, several modifications and improvements may be made without departing from the concept of the present invention, all of which belong to the protection scope of the present invention. The protection scope of the present invention shall be based on the attached claims.

Claims

1. An aromatic amine compound, characterized in that: The structure of the aromatic amine compound is shown in general formula (1): The L1-L3 are independently represented by a direct bond, a substituted or unsubstituted C6-C30 arylene group, or a substituted or unsubstituted 5- to 30-membered heteroarylene group; Said R1 and R2 are independently represented by a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C6-C30 aryl group, or a substituted or unsubstituted 5-30 membered heteroaryl group; The R3, R4, R5, and R6 are the same or different and represent a hydrogen atom, a deuterium atom, a C1-C10 alkyl group, a C3-C20 cycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, or a substituted or unsubstituted 5- to 30-membered heteroaryl group; The R3 and R4, R4 and R5, and R5 and R6 may be bonded to each other to form a C6-C30 aliphatic ring; Ar1 and Ar2 are independently represented by substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 5-30 membered heteroaryl, or C3-C10 cycloalkyl; The substituent replacing the above substitutable group is selected from a deuterium atom, a C1-C10 alkyl group, a C1-C10 alkyl group substituted with a deuterium atom, a C6-C30 aryl group, a C6-C30 aryl group substituted with a deuterium atom, a 5- to 30-membered heteroaryl group, or a 5- to 30-membered heteroaryl group substituted with a deuterium atom; The heteroatom in the heteroaryl group is selected from one or more of oxygen atoms, sulfur atoms and nitrogen atoms; Any hydrogen atom in the general formula (1) may be substituted by a deuterium atom.

2. An aromatic amine compound according to claim 1, characterized in that: The structure of the aromatic amine compound is shown in general formula (2-1): In the general formula (2-1), R1, R2, R3, R4, R5, R6, L1-L3, Ar1, and Ar2 have the same meanings as in the general formula (1).

3. An aromatic amine compound according to claim 1, characterized in that: The structure of the aromatic amine compound is shown in general formula (3-1) or general formula (3-2): In the general formula (3-1) to the general formula (3-2), R1, R2, R3, R4, R5, R6, L1, L2, Ar1, and Ar2 have the same meanings as in the general formula (1).

4. An aromatic amine compound according to claim 1, characterized in that: The structure of the aromatic amine compound is selected from any one of the general formulas (4-1) to (4-6): In general formula (4-1) to general formula (4-6), R3, R4, R5, and R6 are the same or different and represent C1-C10 alkyl, C3-C20 cycloalkyl, substituted or unsubstituted C6-C30 aryl, or substituted or unsubstituted 5- to 30-membered heteroaryl; The R4 and R5 may be bonded to each other to form a C6-C10 aliphatic ring; The L1, L2, Ar1, Ar2, R1 and R2 have the same meanings as in the general formula (1).

5. The aromatic amine organic compound according to claim 1, characterized in that: The structure of the aromatic amine compound is selected from any one of the general formulas (5-1) to (5-16): In the general formulae (5-1) to (5-16), L1, L2, Ar1, and Ar2 have the same meanings as in the general formula (1).

6. The aromatic amine organic compound according to any one of claims 1 to 5, characterized in that: The L1, L2, and L3 are independently represented by a single bond, a substituted or substituted phenylene group, a substituted or unsubstituted naphthylene group, or a substituted or unsubstituted biphenylene group; Ar1 and Ar2 are independently represented by substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted furyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted thienyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted indenyl, substituted or unsubstituted piperonyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted spirofluorenyl, substituted or unsubstituted indolyl, 1,1,4,4-tetramethyl-1,2,3,4-tetrahydronaphthalene, 1,4-benzodioxanyl; R1, R2, R3, R4, R5, and R6 are independently represented by one of hydrogen atom, deuterium atom, methyl group, deuterated methyl group, ethyl group, tert-butyl group, phenyl group, adamantyl group, naphthyl group, and biphenyl group; The substituents replacing the above substitutable groups are selected from one or more of deuterium atoms, methyl, deuterated methyl, ethyl, tert-butyl, adamantyl, phenyl, naphthyl, biphenyl, dibenzofuranyl, carbazolyl, phenanthryl, dibenzothienyl, and benzofuranyl.

7. The aromatic amine organic compound according to any one of claims 1 to 5, characterized in that: The Ar1 and Ar2 are independently represented by the following structures: Any of; The L1, L2, and L3 are independently represented by a single bond or the following structure: Any of the following: * indicates the attachment site.

8. An aromatic amine compound according to claim 1, characterized in that: The structure of the aromatic amine compound is selected from the following structures: Any one of .

9. An organic electroluminescent device, comprising a substrate, a cathode, an anode and an organic functional layer, wherein the organic functional layer is located between the cathode and the anode, and the substrate is adjacent to the cathode or the anode, characterized in that: 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 aromatic amine compound described in any one of claims 1 to 8.

10. The organic electroluminescent device according to claim 9, characterized in that: The hole transport region comprises a hole injection layer, a hole transport layer and a light-emitting auxiliary layer, and the hole injection layer and / or the hole transport layer comprises the aromatic amine compound according to any one of claims 1 to 8.

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