Compound containing azabenzene and spirofluorene structures, organic electroluminescent device and display element

Abstract

The invention discloses a compound containing azabenzene and spirofluorene structures, an organic electroluminescent device and a display element, and belongs to the technical field of semiconductor materials. The compound containing the aza-benzene and spirofluorene structure is shown as a general formula (1): # imgabs0. The compound containing the aza-benzene and spirofluorene structure is applied to a hole blocking layer of an organic electroluminescent device. According to the compound containing the azabenzene and spirofluorene structures, the azabenzene and the spirofluorene structures are bridged through specific ortho-phenyl with substituent groups, so that the compound has excellent hole blocking capability and good material stability, is applied to an organic electroluminescent device, can effectively reduce the working voltage of the device, and can improve the luminous efficiency of the device. And the luminous efficiency and service life of the device are improved.

Description

Technical Field

[0001] The invention relates to the technical field of semiconductor materials, and in particular to a compound containing nitrogen-containing heterobenzene and spirofluorene structures, an organic electroluminescent device and a display element. Background Art

[0002] Organic light-emitting diode (OLED) technology can be used to manufacture new display products as well as new lighting products. It is expected to replace existing liquid crystal displays and fluorescent lighting, and has a wide range of applications. Organic light-emitting diodes have a sandwich-like structure, including electrode material films and organic photoelectric 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 and the electric field acts on the positive and negative charges in the organic photoelectric functional material film layer, the positive and negative charges further recombine in the light-emitting layer, generating organic electroluminescence.

[0003] Currently, organic electroluminescent device display technology has been applied in smart phones, tablet computers, TVs and other fields. However, compared with the actual product application requirements, the performance of organic electroluminescent devices such as luminous efficiency and service life needs to be further improved. In order to continuously improve the performance of organic electroluminescent devices, it is necessary to continuously research and innovate organic optoelectronic functional materials to create higher performance organic optoelectronic functional materials.

[0004] Organic optoelectronic functional materials used in organic electroluminescent devices can be divided into two categories based on their uses, namely charge injection and transport materials and luminescent materials. Furthermore, charge injection and transport materials can be divided into electron injection and transport materials, electron blocking materials, hole injection and transport materials, and hole blocking materials. For organic electroluminescent devices, holes are injected from the anode, electrons are injected from the cathode, and are transported in the organic functional layer, and finally meet in the luminescent layer to form excitons, which recombine and emit light. The hole blocking layer is located between the luminescent layer and the electron transport layer, which can block the diffusion or movement of holes to the electron transport layer, and can also reduce the energy loss of excitons, playing a role in interface modification and auxiliary regulation of electron injection / transport. Due to the poor electron regulation ability and hole and exciton blocking ability of the existing hole blocking layer materials, it is difficult to obtain an efficient electron-hole balance inside the light-emitting layer, and it is difficult to obtain low-voltage, high-efficiency, and long-life devices. At the same time, the existing hole blocking layer materials also have a narrow heat resistance window and poor electron tolerance. Therefore, it is necessary to further improve the electron injection and transmission capabilities of the hole blocking layer materials, the hole and exciton blocking ability, enhance the stability of the material, reduce the device's turn-on voltage and driving voltage, achieve an efficient balance of excitons, and improve the device's efficiency and device life. Summary of the invention

[0005] In view of the above problems existing in the prior art, the present invention provides a compound containing nitrogen-containing benzene and spirofluorene structures, an organic electroluminescent device and a display element. The nitrogen-containing benzene and spirofluorene in the present invention are bridged by a specific ortho-phenyl group having a substituent, so that the compound has excellent hole blocking ability and good material stability. When applied to organic electroluminescent devices, it can effectively reduce the operating voltage of the device and improve the luminous efficiency and service life of the device.

[0006] The technical solution of the present invention is as follows: a compound containing nitrogen-containing heterobenzene and spirofluorene structures, wherein the compound containing nitrogen-containing heterobenzene and spirofluorene structures is shown in the general formula (1):

[0007]

[0008] In the general formula (1), X1, X2, and X3 are each independently CH or N; at least one of X1, X2, and X3 is N;

[0009] Ar represents any one of the following groups: substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted carbazolyl;

[0010] R1 represents any one of the following groups: substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted pyridyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothienyl; Ar and R1 are the same or different;

[0011] * represents the connection position; that is, the compound containing nitrogen-containing heterobenzene and spirofluorene structure is any one of the general formula (1-1) and general formula (1-2):

[0012]

[0013] R represents the structure shown in general formula (2);

[0014]

[0015] Ring B is represented by a substituted or unsubstituted phenyl group, or a substituted or unsubstituted naphthyl group; any unsubstituted carbon on the benzene ring or naphthalene ring in the general formula (2) can serve as a connection site with the general formula (1);

[0016] The substituent of the substituted group is a deuterium atom, a cyano group, a phenyl group, a biphenyl group, a naphthyl group, a pyridyl group, a pyrimidyl group or a pyridazinyl group.

[0017] Furthermore, the compound containing nitrogen-containing heterobenzene and spirofluorene structures is represented by any one of the general formulas (2-1) to (2-6):

[0018] In the general formulae (2-1) to (2-6), X1, X2, X3, Ar, R1 and ring B have the same meanings as in the general formula (1).

[0019] Furthermore, the general formula (2) is represented by any one of the general formulas a, b, c and d:

[0020]

[0021] In the general formula a, R2 represents a hydrogen atom, a cyano group, a phenyl group, a biphenyl group, a naphthyl group, a pyridyl group, a pyrimidyl group, a pyridazinyl group or a pyrazinyl group;

[0022] Preferably, the general formula (2) is represented by any one of the following structures:

[0023]

[0024] Further, the general formula (2) is represented by any one of the following structures:

[0025]

[0026] The R2 represents a hydrogen atom, a cyano group, a phenyl group, a biphenyl group, a naphthyl group, a pyridyl group, a pyrimidyl group, a pyridazinyl group or a pyrazinyl group;

[0027] In the general formula a-1, the connection site with the general formula (1) is 1, 2, 3 or 4; the connection site of R2 is 5, 6, 7, 8, 9, 10, 11 or 12;

[0028] In the general formula a-2, the connection site with the general formula (1) is 5, 6, 7, 8, 9, 10, 11 or 12; the connection site of R2 is 5, 6, 7, 8, 9, 10, 11 or 12;

[0029] In the general formula b-1, the connection site with the general formula (1) is 1', 2', 3' or 4';

[0030] In the general formula b-2, the connection site with the general formula (1) is 5', 6', 7', 8', 9', 10', 11', 12', 13' or 14';

[0031] In the general formula c-1, the connection site with the general formula (1) is 1", 2", 3" or 4";

[0032] In the general formula c-2, the connection site with the general formula (1) is 5", 6", 7", 8", 9", 10", 11", 12", 13" or 14";

[0033] In the general formula d-1, the connection site with the general formula (1) is 1"', 2"', 3"' or 4"';

[0034] In the general formula d-2, the connection site with the general formula (1) is 5"', 6"', 7"', 8"', 9"', 10"', 11"', 12"', 13"' or 14"';

[0035] Furthermore, in the general formula (1), at least two of X1, X2, and X3 are represented by N.

[0036] Preferably, in the general formula (1), X1, X2, and X3 are all represented by N.

[0037] Further, Ar is selected from the following structures:

[0038] Any of;

[0039] The R1 is selected from the following structures:

[0040] Any one of.

[0041] Furthermore, the compound containing nitrogen-containing heterobenzene and spirofluorene structures is any one of the following structures:

[0042]

[0043]

[0044]

[0045]

[0046]

[0047]

[0048]

[0049]

[0050]

[0051]

[0052]

[0053]

[0054]

[0055]

[0056]

[0057]

[0058]

[0059]

[0060]

[0061]

[0062]

[0063]

[0064] The invention also discloses an organic electroluminescent device, comprising a substrate, a first electrode and a second electrode, wherein a multilayer organic film layer is provided between the first electrode and the second electrode, and the organic film layer contains the nitrogen-containing heterobenzene and spirofluorene structure compounds of the invention.

[0065] Furthermore, the organic thin film layer includes a hole transport region thin film layer, a light emitting region thin film layer and an electron transport region thin film layer, and the electron transport region thin film layer contains the nitrogen-containing heterobenzene and spirofluorene structure compounds.

[0066] Furthermore, the electron transport region thin film layer comprises a hole blocking layer, and the hole blocking layer contains the nitrogen-containing heterobenzene and spirofluorene structure compounds.

[0067] Furthermore, the hole transport region thin film layer comprises a hole injection layer, a hole transport layer and an electron blocking layer, the electron transport region thin film layer comprises a hole blocking layer, an electron transport layer and an electron injection layer, and the hole blocking layer contains the nitrogen-containing heterobenzene and spirofluorene structure compounds.

[0068] The invention also discloses a display element, which contains the organic electroluminescent device of the invention.

[0069] The beneficial technical effects of the present invention are:

[0070] The azabenzene structure and the spirofluorene structure of the present invention are connected by a special bridging method, so that the compound protected by the present invention has more excellent hole blocking and exciton blocking capabilities, can effectively block the holes from diffusing or moving to the electron transport layer, so that the holes are better confined in the light-emitting area, ensuring that more excitons are formed by holes and electrons in the light-emitting layer, increasing the exciton concentration, and thus improving the luminous efficiency and device life.

[0071] The azabenzene structure and the spirofluorene structure protected by the present invention are bridged by a substituted phenyl group, and the connection position is the ortho position, thereby forming a twisted molecule with a special spatial stereo configuration. Therefore, the compound protected by the present invention has a more excellent electron regulation ability, supplements the electron transport layer, and improves or delays electron injection and transmission according to the electron-hole balance in the light-emitting layer, thereby improving the luminous efficiency and life of the device.

[0072] The nitrogen-containing heterobenzene and spirofluorene structure compounds protected by the present invention have lower evaporation temperature and chemical stability, so that the evaporation film thereof has good film phase stability and a wider heat resistance window, thereby ensuring the stability in device manufacturing and product use. BRIEF DESCRIPTION OF THE DRAWINGS

[0073] Figure 1 Schematic diagram of the structure of the organic electroluminescent device described in the embodiment.

[0074] In the figure, 1, transparent substrate layer; 2, anode layer; 3, hole injection layer; 4, hole transport layer; 5, electron blocking layer; 6, light-emitting layer; 7, hole blocking layer; 8, electron transport layer; 9, electron injection layer; 10, cathode layer; 11, light extraction layer. DETAILED DESCRIPTION

[0075] The specific implementation of the present invention is described in detail below. The present invention can be implemented in many other ways than those described herein, and those skilled in the art can make similar improvements without violating the connotation of the present invention, so the present invention is not limited by the specific embodiments disclosed.

[0076] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which the present invention belongs. The terms used are only for describing specific embodiments and are not intended to limit the present invention.

[0077] In this application, unless otherwise specified, HOMO means the highest occupied orbital of a molecule, and LUMO means the lowest unoccupied orbital of a molecule. In addition, in the present invention, HOMO and LUMO energy levels are expressed in absolute values, and the comparison between energy levels is also a comparison of the magnitude of their absolute values. Those skilled in the art know that the greater the absolute value of an energy level, the lower the energy of the energy level.

[0078] In the accompanying drawings, the dimensions of layers and regions may be exaggerated for clarity. It will also be understood that when a layer or element is referred to as being "above" another layer or substrate, the layer or element may be directly above the other layer or substrate, or there may be intervening layers. 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 there may be one or more intervening layers. The same reference numerals throughout the text represent the same elements.

[0079] In this application, when describing electrodes and organic electroluminescent devices, as well as other structures, the words "upper" and "lower" used to indicate orientation only indicate orientation in a certain state, and do not mean that the related structure can only exist in the described orientation; on the contrary, if the structure can change its position, such as being inverted, the orientation of the structure will be changed accordingly. Specifically, in the present invention, the "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 "upper" side.

[0080] Organic electroluminescent devices:

[0081] In another embodiment of the present application, an organic electroluminescent device is provided, which includes a first electrode (anode), a second electrode (cathode), and a plurality of organic thin film layers located between the first electrode and the second electrode, wherein at least one organic thin film layer contains the nitrogen-containing heterobenzene and spirofluorene structure compounds.

[0082] In a preferred embodiment of the present application, the organic thin film layer comprises a hole blocking layer, wherein the hole blocking layer comprises the nitrogen-containing heterobenzene and spirofluorene structured compounds according to the present invention.

[0083] In a preferred embodiment of the present invention, the organic electroluminescent device according to the present invention comprises a substrate, a first electrode layer (anode layer), an organic thin film layer, a second electrode layer (cathode layer), wherein the organic thin film layer includes, but is not limited to, a light-emitting layer and a hole injection layer, a hole transport layer, an electron blocking layer, an electron transport layer, an electron injection layer, a second electrode (cathode) and a CPL layer (light extraction layer).

[0084] The preferred device structure of the present invention adopts the top emitting form. Preferably, the anode of the organic electroluminescent device of the present invention adopts an electrode with high reflectivity, preferably ITO / Ag / ITO; the cathode adopts a transparent electrode, preferably a mixed electrode of Mg:Ag=1:9, thereby forming a microcavity resonance effect, and the device emits light from the Mg:Ag electrode side.

[0085] In a preferred embodiment of the present invention, an organic electroluminescent device is provided, which includes a substrate, an anode, a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, a cathode layer and a CPL layer, wherein the anode is above the substrate, the hole injection layer is above the anode, the hole transport layer is above the hole injection layer, the electron blocking layer is above the hole transport layer, the light-emitting layer is above the hole transport layer, the hole blocking layer is above the light-emitting layer, the electron transport layer is above the hole blocking layer, the electron injection layer is above the electron transport layer, the cathode layer is above the electron injection layer, and the CPL layer is above the cathode layer.

[0086] As the substrate of the organic electroluminescent device of the present invention, any substrate commonly used in organic electroluminescent devices can be used. Examples are transparent substrates such as glass or transparent plastic substrates; opaque substrates such as silicon substrates; flexible PI film substrates. Different substrates have different mechanical strengths, thermal stability, transparency, surface smoothness, and waterproofness. Depending on the properties of the substrate, its use direction is different. In the present invention, a transparent substrate is preferably used. The thickness of the substrate is not particularly limited.

[0087] A first electrode (anode) is formed on a substrate, and the anode material is preferably a material with a high work function so that holes are easily injected into the organic functional material layer. Non-limiting examples of anode materials include, but are not limited to, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO2), zinc oxide (ZnO), magnesium (Mg), aluminum (Al), silver (Ag), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In) and magnesium-silver (Mg-Ag). The first electrode can have a single-layer structure or a multilayer structure including two or more layers. For example, the anode can have a three-layer structure of ITO / Ag / ITO, but is not limited thereto. In addition, the thickness of the anode depends on the material used, typically 50-500nm, preferably 70-300nm, and more preferably 100-200nm.

[0088] A hole injection layer, a hole transport layer, and an electron blocking layer may be disposed between the anode layer and the light emitting layer.

[0089] The hole injection layer structure is that the hole injection layer material is uniformly or non-uniformly dispersed in the hole transport layer, and the hole injection material can be, for example, a P dopant. The P dopant can be selected from at least one compound selected from the following: a quinone derivative, such as tetracyanoquinodimethane (TCNQ) or 2,3,5,6-tetrafluoro-tetracyano-1,4-benzoquinodimethane (F4-TCNQ); a metal oxide, such as tungsten oxide or molybdenum oxide; or a cyano-containing compound, such as the compounds P1, NDP and F4-TCNQ shown below:

[0090]

[0091] According to the present invention, P1 is preferably used as the P dopant. The ratio of the hole transport layer to the P dopant used in the present invention is 99:1-70:30, preferably 99:1-85:15, and more preferably 97:3-87:13, based on mass.

[0092] The thickness of the hole injection layer of the present invention may be 1-100 nm, preferably 2-50 nm, and more preferably 5-20 nm.

[0093] The material of the hole transport layer is preferably a material having a high hole mobility, which enables holes to be transferred from the anode or the hole injection layer to the light-emitting layer. The hole transport material can be a phthalocyanine derivative, a triazole derivative, a triarylmethane derivative, a triarylamine derivative, an oxazole derivative, an oxadiazole derivative, a hydrazone derivative, a stilbene derivative, a pyridoline derivative, a polysilane derivative, an imidazole derivative, a phenylenediamine derivative, an amino-substituted quilone derivative, a styrene anthracene derivative, a styrene compound such as a styrene amine derivative, a fluorene derivative, a spirofluorene derivative, a silazane derivative, an aniline copolymer, a porphyrin compound, a carbazole derivative, a polyarylalkane derivative, polyphenylene vinyl and its derivatives, polythiophene and its derivatives, poly-N-vinylcarbazole derivatives, thiophene oligomers and other conductive polymer oligomers, aromatic tertiary amine compounds, styrene amination compounds, etc. compounds, triamines, tetraamines, benzidines, propargyl diamine derivatives, p-phenylenediamine derivatives, m-phenylenediamine derivatives, 1,1'-bis(4-diarylaminophenyl)cyclohexane, 4,4'-bis(diarylamino)biphenyls, bis[4-(diarylamino)phenyl]methanes, 4,4"-bis(diarylamino)terphenyls, 4,4'"-bis(diarylamino)quaterphenyls, 4,4'-bis(diarylamino)diphenyl ethers, 4,4'-bis(diarylamino)diphenylsulfanes, bis[4-(diarylamino)phenyl]dimethylmethanes, bis[4-(diarylamino)phenyl]-bis(trifluoromethyl)methanes or 2,2-diphenylethylene compounds, etc.

[0094] The thickness of the hole transport layer of the present invention may be 5-200 nm, preferably 10-180 nm, and more preferably 20-150 nm.

[0095] The electron blocking layer requires that the triplet state (T1) energy level of the material is higher than the T1 energy level of the main material in the light-emitting layer, which can play a role in blocking the energy loss of the light-emitting layer material; the HOMO energy level of the electron blocking layer material is between the HOMO energy level of the hole transport layer material and the HOMO energy level of the main material of the light-emitting layer, which is conducive to the injection of holes from the positive electrode into the light-emitting layer. At the same time, the electron blocking layer material is required to have a high hole mobility, which is conducive to hole transport and reduces the power of the device; the LUMO energy level of the electron blocking layer material is higher than the LUMO energy level of the main material of the light-emitting layer, which plays a role in electron blocking, that is, the electron blocking layer material is required to have a wide bandgap width (Eg). The electron blocking layer materials that meet the above conditions can be triarylamine derivatives, fluorene derivatives, spirofluorene derivatives, dibenzofuran derivatives, carbazole derivatives, etc. Among them, triarylamine derivatives are preferred, such as N4,N4-bis([1,1'-biphenyl]-4-yl)-N4'-phenyl N4'-[1,1':4',1"-terphenyl]-4-yl-[1,1'-biphenyl]-4,4'-diamine; spirofluorene derivatives, such as N-([1,1'-diphenyl]-4-yl)-N-(9,9-dimethyl-9H-furan-2-yl)-9,9'-spirobifluorene-2-amine; dibenzofuran derivatives, such as N,N-di([1,1'-biphenyl]-4-yl)-3'-(dibenzo[b,d]furan-4-yl)-[1,1'-biphenyl]-4-amine, but are not limited to these.

[0096] According to the present invention, the thickness of the electron blocking layer may be 1-200 nm, preferably 5-150 nm.

[0097] According to the present invention, the light-emitting layer is located between the first electrode and the second electrode. The material of the light-emitting layer is a material that can emit visible light by receiving holes from the hole transport region and electrons from the electron transport region respectively, and combining the received holes and electrons. The light-emitting layer may include a host material and a doping material. As the host material and guest material of the light-emitting layer of the organic electroluminescent device of the present invention, the host material may be one or a combination of two of anthracene derivatives, quinoxaline derivatives, triazine derivatives, xanthone derivatives, diphenyl ketone derivatives, carbazole derivatives, pyridine derivatives or pyrimidine derivatives. The guest material may be a pyrene derivative, a boron derivative, a chrysene derivative, a spirofluorene derivative, an iridium complex or a platinum complex.

[0098] The hole blocking layer can be arranged on the light-emitting layer. The triplet state (T1) energy level of the hole blocking layer material is higher than the T1 energy level of the main material of the light-emitting layer, which can play a role in blocking the energy loss of the light-emitting layer material; the HOMO energy level of the material is lower than the HOMO energy level of the main material of the light-emitting layer, which plays a role in hole blocking. At the same time, the hole blocking layer material is required to have high electron injection and hole blocking capabilities, which is conducive to electron transmission and reduces the application power of the device.

[0099] The thickness of the hole blocking layer of the present invention may be 2-200 nm, preferably 5-150 nm, but the thickness is not limited to this range.

[0100] The electron transport layer may be disposed on 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.

[0101] The electron injection layer material is preferably metal Yb with a low work function, so that electrons are easily injected into the organic functional material layer. 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.

[0102] The second electrode can be a cathode, and the material for forming the cathode can be a material with a low work function, such as a metal, an alloy, a conductive compound, or a mixture thereof. Non-limiting examples of cathode materials can include lithium (Li), ytterbium (Yb), magnesium (Mg), aluminum (Al), calcium (Ca), and aluminum-lithium (Al-Li), magnesium-indium (Mg-In) and magnesium-silver (Mg-Ag). The thickness of the cathode depends on the material used, typically 5-100nm, preferably 7-50nm and more preferably 10-25nm.

[0103] Optionally, in order to improve the light extraction efficiency of the organic electroluminescent device, a light extraction layer (i.e., CPL layer) may be added on the second electrode (i.e., cathode) of the device. According to the optical absorption and refraction principle, the refractive index of the CPL layer material should be as high as possible, and the absorption coefficient should be as small as possible. Any material known in the art can be used as the CPL layer material, such as Alq3. The thickness of the CPL layer is generally 5-300 nm, preferably 20-100 nm, and more preferably 40-80 nm.

[0104] Optionally, the organic electroluminescent device 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 film covering the entire surface of the organic layer.

[0105] Organic electroluminescent device preparation method:

[0106] The present invention also relates to a method for preparing the above-mentioned organic electroluminescent device, which comprises laminating a first electrode, a multi-layer organic thin film layer and a second electrode on a substrate in sequence. The multi-layer organic thin film layer is formed by laminating a hole transport region, a light-emitting layer and a hole blocking region on the first electrode from bottom to top, and the hole transport region is formed by laminating a hole injection layer, a hole transport layer and an electron blocking layer on the first electrode in sequence from bottom to top, and the hole blocking region is formed by laminating a hole blocking layer, an electron transport layer and an electron injection layer on the light-emitting layer in sequence from bottom to top. In addition, optionally, a CPL layer can also be laminated on the second electrode to improve the light extraction efficiency of the organic electroluminescent device.

[0107] For lamination, vacuum deposition, vacuum evaporation, spin coating, casting, LB method, inkjet printing, laser printing or LITI methods may be used, but are not limited thereto. Vacuum evaporation means heating and coating a material onto a substrate in a vacuum environment.

[0108] In the present invention, the various layers are preferably formed by vacuum evaporation, wherein the layers can be formed at a temperature of about 100-500° C. and at a temperature of about 10 -8 -10 -2 Torr vacuum and approx. The vacuum evaporation is carried out at a rate of 10 -6 -10 -2 Torr, preferably 10 -5 -10 -3 Torr.

[0109] The rate is about More preferably, about

[0110] 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.

[0111] Display components:

[0112] The present invention also relates to a display device including the above-mentioned organic electroluminescent device, in particular a flat panel display device. In a preferred embodiment, the display device may include one or more of the above-mentioned organic electroluminescent devices, and in the case of including a plurality of devices, the devices are stacked and combined laterally or longitudinally. The display device may also include at least one thin film transistor. The thin film transistor may include a gate electrode, a source electrode and a drain electrode, a gate insulating layer and an active layer, wherein one of the source electrode and the drain electrode may be electrically connected to the first electrode of the organic electroluminescent device. The active layer may include crystalline silicon, amorphous silicon, an organic semiconductor or an oxide semiconductor, but is not limited thereto.

[0113] The following examples are intended to better explain the present invention, but the scope of the present invention is not limited thereto.

[0114] I. Compound Preparation Examples

[0115] The raw materials involved in the synthesis examples of the present invention can be purchased from the market or prepared by conventional preparation methods in the art;

[0116] Preparation of intermediate C1, intermediate E1, intermediate F1:

[0117]

[0118] Under nitrogen protection, in a 500 ml round-bottom flask, raw material A1 (6.35 g, 20 mmol), raw material BB1 (2.46 g, 20.2 mmol), K2CO3 (8.29 g, 60 mmol), ethylene glycol dimethyl ether (150 mL), water (25 mL) were added in sequence, nitrogen was passed through for 30 min to replace the air, bistriphenylphosphine palladium dichloride PdCl2(PPh3)2 (0.42 g, 0.6 mmol) was added, and the mixture was heated to reflux for 10 h under nitrogen protection. The reaction solution was taken for TCL detection to find that the raw material A1 was completely reacted. After the reaction was completed, the reaction system was naturally cooled to room temperature, the solvent was removed by rotary evaporation, 150 ml of dichloromethane was added to the residue to dissolve, 100 ml of water was added to wash, poured into a separatory funnel and shaken, and then allowed to stand for stratification. After separation, the aqueous phase was extracted with dichloromethane (50 ml*3), the organic phases were combined and dried with anhydrous magnesium sulfate, filtered, and the filtrate was subjected to rotary evaporation to remove ethyl acetate to obtain a crude product, which was purified by silica gel column chromatography to obtain intermediate C1. LC-MS: Measured value: 266.62 ([M+H] + ); exact mass: 265.95.

[0119] Under nitrogen protection, in a 250 ml round-bottom flask, raw material D1 (6.19 g, 18 mmol), diboronic acid pinacol ester (5.08 g, 20 mmol), potassium acetate (5.30 g, 54 mmol), N,N-dimethylformamide DMF (100 mL) were added in sequence, nitrogen was passed through for 30 min to replace the air, [1,1'-bis(diphenylphosphino)ferrocene] dichloropalladium dichloromethane complex PdCl2(dppf)CH2Cl2 (0.73 g, 0.9 mmol) was added, and the mixture was heated to reflux for 16 h under nitrogen protection. The reaction solution was taken for TCL detection, and it was found that the raw material D1 had reacted completely. After the reaction was completed, the reaction system was naturally cooled to room temperature, and the solvent was removed by rotary evaporation. The residue was added into 150 ml of ethyl acetate to dissolve, and 100 ml of water was added for washing. After pouring into a separatory funnel and shaking, the mixture was allowed to stand for stratification. After separation, the aqueous phase was extracted with ethyl acetate (50 ml*3), and the organic phases were combined and dried with anhydrous magnesium sulfate, filtered, and the filtrate was subjected to rotary evaporation to remove ethyl acetate to obtain the intermediate E1. LC-MS: Measured value: 436.18 ([M+H] + ); exact mass: 435.21.

[0120] Under nitrogen protection, in a 500 ml round-bottom flask, intermediate C1 (4.01 g, 15 mmol), intermediate E1 (5.19 g, 15.1 mmol), K2CO3 (6.22 g, 45 mmol), tetrahydrofuran (120 mL), water (60 mL) were added in sequence, and nitrogen was passed through for 30 min to replace the air. Palladium acetate (CAS: 3375-31-3) (0.10 g, 0.45 mmol) and n-butyldi(1-adamantyl)phosphine (CAS: 321921-71-5) (0.48 g, 1.35 mmol) were added, and the mixture was heated to reflux for 18 h under nitrogen protection. The reaction solution was taken for TCL detection and it was found that the intermediate C1 reacted completely. After the reaction was completed, the reaction system was naturally cooled to room temperature, the solvent was removed by rotary evaporation, 120 ml of dichloromethane was added to the residue to dissolve, 80 ml of water was added to wash, poured into a separatory funnel and shaken, and then allowed to stand for stratification. After separation, the aqueous phase was extracted with dichloromethane (50 ml*3), the organic phases were combined and dried with anhydrous magnesium sulfate, filtered, and the filtrate was subjected to rotary evaporation to remove dichloromethane to obtain a crude product, which was purified by silica gel chromatography to obtain intermediate F1. LC-MS: Measured value: 496.41 ([M+H] + ); exact mass: 495.15.

[0121] Intermediate C was prepared by the synthesis method of intermediate C1, except that different raw materials were replaced. The raw materials A and B used are shown in Table 1;

[0122] Intermediate E was prepared by the synthesis method of intermediate E1, except that different raw materials were replaced. The raw material D used is shown in Table 2;

[0123] Intermediate F was prepared by the synthesis method of intermediate F1, except that different intermediates were used as raw materials. The intermediates C and E used are shown in Table 1;

[0124] Table 1

[0125]

[0126]

[0127]

[0128]

[0129] Example 1: Synthesis of Compound 2

[0130]

[0131] Under nitrogen protection, in a 250 ml round-bottom flask, intermediate F1 (4.96 g, 10 mmol), raw material H1 (5.31 g, 12 mmol), K2CO3 (4.15 g, 30 mmol), tetrahydrofuran (90 mL), water (30 mL) were added in sequence, nitrogen was passed for 30 min to replace the air, Pd (PPh3) 4 (0.58 g, 0.5 mmol) was added, and the mixture was heated under reflux for 18 h under nitrogen protection. The reaction solution was taken for TCL detection to find that the reaction of intermediate F1 was complete. After the reaction was completed, the reaction system was naturally cooled to room temperature, the solvent was removed by rotary evaporation, 100 ml of chloroform was added to the residue to dissolve, 100 ml of water was added to wash, poured into a separating funnel and shaken, and then allowed to stand for stratification. After separation, the aqueous phase was extracted with dichloromethane (80 ml * 3), the organic phases were combined and dried with anhydrous magnesium sulfate, filtered, and the filtrate was evaporated to remove chloroform to obtain a crude product, which was purified by silica gel column chromatography to obtain compound 2. Elemental analysis: C 58 H 37 N3; theoretical value: C, 89.78; H, 4.81; N, 5.42; test value: C, 89.74; H, 4.87; N, 5.39. LC-MS: measured value: 776.44 ([M+H] + ), exact mass: 775.30.

[0132] Example 2: Synthesis of Compound 6

[0133]

[0134] Compound 6 was prepared according to the synthesis method of compound 2 in Example 1, except that intermediate F2 was used to replace intermediate F1. Elemental analysis: C 58 H 37N3; Theoretical value: C, 89.78; H, 4.81; N, 5.42; Test value: C, 89.71; H, 4.85; N, 5.44. LC-MS: Found: 776.27 ([M+H]+), Exact mass: 775.30.

[0135] Example 3: Synthesis of Compound 9

[0136]

[0137] Compound 9 was prepared according to the synthetic method of compound 2 in Example 1, except that intermediate F3 was used to replace intermediate F1, and raw material H2 was used to replace raw material H1. Elemental analysis: C 58 H 37 N3; theoretical value: C, 89.78; H, 4.81; N, 5.42; test value: C, 89.75; H, 4.80; N, 5.46. LC-MS: measured value: 776.05 ([M+H] + ), exact mass: 775.30.

[0138] Example 4: Synthesis of Compound 10

[0139]

[0140] Compound 10 was prepared according to the synthesis method of compound 2 in Example 1, except that intermediate F3 was used to replace intermediate F1. Elemental analysis: C 58 H 37 N3; theoretical value: C, 89.78; H, 4.81; N, 5.42; test value: C, 89.65; H, 4.86; N, 5.52. LC-MS: measured value: 776.14 ([M+H] + ), exact mass: 775.30.

[0141] Example 5: Synthesis of Compound 26

[0142]

[0143] Compound 26 was prepared according to the synthesis method of compound 2 in Example 1, except that intermediate F5 was used to replace intermediate F1. Elemental analysis: C 56 H 35 N3; Calculated value: C, 89.69; H, 4.70; N, 5.60; Test value: C, 89.62; H, 4.78; N, 5.58. LC-MS: Measured value: 750.37 ([M+H]+), exact mass: 749.28.

[0144] Example 6: Synthesis of Compound 38

[0145]

[0146] Compound 38 was prepared according to the synthetic method of compound 2 in Example 1, except that intermediate F6 was used to replace intermediate F1. Elemental analysis: C 56 H 35 N3; Theoretical value: C, 89.69; H, 4.70; N, 5.60; Test value: C, 89.78; H, 4.66; N, 5.55. LC-MS: Measured value: 750.45 ([M+H]+), exact mass: 749.28.

[0147] Example 7: Synthesis of Compound 85

[0148]

[0149] Compound 85 was prepared according to the synthesis method of compound 2 in Example 1, except that intermediate F7 was used to replace intermediate F1. Elemental analysis: C 53 H 32 N4; Calculated: C, 87.82; H, 4.45; N, 7.73; Measured: C, 87.86; H, 4.40; N, 7.76. LC-MS: Measured: 725.45 ([M+H]+), Exact mass: 724.26.

[0150] Example 8: Synthesis of Compound 106

[0151]

[0152] Compound 106 was prepared according to the synthetic method of compound 2 in Example 1, except that intermediate F8 was used to replace intermediate F1, and raw material H2 was used to replace raw material H1. Elemental analysis: C 59 H 36 N4; Calculated: C, 88.47; H, 4.53; N, 7.00; Measured: C, 88.41; H, 4.56; N, 7.03. LC-MS: Measured: 801.22 ([M+H]+), Exact mass: 800.29. C, 88.47; H, 4.53; N, 7.00

[0153] Example 9: Synthesis of Compound 128

[0154]

[0155] Compound 128 was prepared according to the synthetic method of compound 2 in Example 1, except that intermediate F9 was used to replace intermediate F1, and raw material H3 was used to replace raw material H1. Elemental analysis: C 60 H 37N3; Theoretical value: C, 90.09; H, 4.66; N, 5.25; Test value: C, 90.00; H, 4.78; N, 5.22. LC-MS: Found: 800.02 ([M+H]+), Exact mass: 799.30.

[0156] Example 10: Synthesis of Compound 152

[0157]

[0158] Compound 152 was prepared according to the synthesis method of compound 2 in Example 1, except that intermediate F10 was used to replace intermediate F1. Elemental analysis: C 58 H 37 N3; Calculated: C, 89.78; H, 4.81; N, 5.42; Measured: C, 89.60; H, 4.89; N, 5.49. LC-MS: Measured: 776.34 ([M+H]+), Exact mass: 775.30.

[0159] Example 11: Synthesis of Compound 173

[0160]

[0161] Compound 173 was prepared according to the synthesis method of compound 2 in Example 1, except that intermediate F11 was used to replace intermediate F1. Elemental analysis: C 56 H 35 N3; Theoretical value: C, 89.69; H, 4.70; N, 5.60; Test value: C, 89.82; H, 4.85; N, 5.38. LC-MS: Measured value: 750.35 ([M+H]+), exact mass: 749.28.

[0162] Example 12: Synthesis of Compound 177

[0163]

[0164] Compound 177 was prepared according to the synthetic method of compound 2 in Example 1, except that intermediate F12 was used to replace intermediate F1. Elemental analysis: C 56 H 35 N3; theoretical value: C, 89.69; H, 4.70; N, 5.60; measured value: C, 89.72; H, 4.82; N, 5.44. LC-MS: measured value: 750.33 ([M+H] + ), exact mass: 749.28.

[0165] Example 13: Synthesis of Compound 189

[0166]

[0167] Compound 189 was prepared according to the synthetic method of compound 2 in Example 1, except that intermediate F13 was used to replace intermediate F1, and raw material H2 was used to replace raw material H1. Elemental analysis: C 51 H 32 N4; Calculated: C, 87.40; H, 4.60; N, 7.99; Measured: C, 87.43; H, 4.65; N, 7.92. LC-MS: Measured: 701.55 ([M+H]+), Exact mass: 700.26.

[0168] Example 14: Synthesis of Compound 202

[0169]

[0170] Compound 202 was prepared according to the synthetic method of compound 2 in Example 1, except that intermediate F14 was used to replace intermediate F1. Elemental analysis: C 53 H 32 N4; theoretical value: C, 87.82; H, 4.45; N, 7.73; test value: C, 87.81; H, 4.57; N, 7.61. LC-MS: measured value: 725.15 ([M+H] + ), exact mass: 724.26.

[0171] Example 15: Synthesis of Compound 214

[0172]

[0173] Compound 214 was prepared according to the synthetic method of compound 2 in Example 1, except that intermediate F15 was used to replace intermediate F1, and raw material H4 was used to replace intermediate H1. Elemental analysis: C 56 H 35 N3; theoretical value: C, 89.69; H, 4.70; N, 5.60; test value: C, 89.63; H, 4.88; N, 5.49. LC-MS: measured value: 750.11 ([M+H] + ), exact mass: 749.28.

[0174] Example 16: Synthesis of Compound 218

[0175]

[0176] Compound 218 was prepared according to the synthetic method of compound 2 in Example 1, except that intermediate F15 was used to replace intermediate F1, and raw material H5 was used to replace intermediate H1. Elemental analysis: C 56 H 35N3; Theoretical value: C, 89.69; H, 4.70; N, 5.60; Test value: C, 89.47; H, 4.90; N, 5.65. LC-MS: Measured value: 750.08 ([M+H]+), exact mass: 749.28.

[0177] Example 17: Synthesis of Compound 222

[0178]

[0179] Compound 222 was prepared according to the synthetic method of compound 2 in Example 1, except that intermediate F15 was used to replace intermediate F1, and raw material H6 was used to replace intermediate H1. Elemental analysis: C 56 H 35 N3; theoretical value: C, 89.69; H, 4.70; N, 5.60; test value: C, 89.55; H, 4.75; N, 5.73. LC-MS: measured value: 750.19 ([M+H] + ), exact mass: 749.28.

[0180] Example 18: Synthesis of Compound 236

[0181]

[0182] Compound 236 was prepared according to the synthesis method of compound 2 in Example 1, except that intermediate F16 was used to replace intermediate F1, and raw material H6 was used to replace intermediate H1. Elemental analysis: C 56 H 35 N3; theoretical value: C, 89.69; H, 4.70; N, 5.60; test value: C, 89.87; H, 4.59; N, 5.57. LC-MS: measured value: 750.23 ([M+H] + ), exact mass: 749.28.

[0183] Example 19: Synthesis of Compound 247

[0184]

[0185] Compound 247 was prepared according to the synthetic method of compound 2 in Example 1, except that intermediate F17 was used to replace intermediate F1. Elemental analysis: C 59 H 38 N2; theoretical value: C, 91.44; H, 4.94; N, 3.61; test value: C, 91.48; H, 4.99; N, 3.63. LC-MS: Found: 775.37 ([M+H] + ), exact mass: 774.30.

[0186] Example 20: Synthesis of Compound 297

[0187]

[0188] Compound 297 was prepared according to the synthetic method of compound 2 in Example 1, except that intermediate 18 was used to replace intermediate F1, and raw material H6 was used to replace raw material H1. Elemental analysis: C 59 H 38 N2; theoretical value: C, 91.44; H, 4.94; N, 3.61; test value: C, 91.52; H, 4.83; N, 3.67. LC-MS: measured value: 775.16 ([M+H] + ), exact mass: 774.30.

[0189] Example 21: Synthesis of Compound 377

[0190]

[0191] Compound 377 was prepared according to the synthesis method of compound 2 in Example 1, except that intermediate F19 was used to replace intermediate F1. Elemental analysis: C 57 H 36 N2; theoretical value: C, 91.41; H, 4.85; N, 3.74; test value: C, 91.45; H, 4.89; N, 3.69. LC-MS: Found: 749.04 ([M+H] + ), exact mass: 748.29.

[0192] Example 22: Synthesis of Compound 384

[0193]

[0194] Compound 384 was prepared according to the synthetic method of compound 2 in Example 1, except that intermediate F20 was used to replace intermediate F1, and raw material H2 was used to replace H1. Elemental analysis: C 57 H 36 N2; theoretical value: C, 91.41; H, 4.85; N, 3.74; test value: C, 91.36; H, 4.79; N, 3.86. LC-MS: Found: 749.33 ([M+H] + ), exact mass: 748.29.

[0195] Example 23: Synthesis of Compound 401

[0196]

[0197] Compound 401 was prepared according to the synthesis method of compound 2 in Example 1, except that intermediate F21 was used to replace intermediate F1. Elemental analysis: C 52 H 33 N3; theoretical value: C, 89.24; H, 4.75; N, 6.00; test value: C, 89.21; H, 4.71; N, 6.08. LC-MS: found value: 700.16 ([M+H] + ), exact mass: 699.27.

[0198] Example 24: Synthesis of Compound 424

[0199]

[0200] Compound 424 was prepared according to the synthesis method of compound 2 in Example 1, except that intermediate F22 was used to replace intermediate F1. Elemental analysis: C 54 H 33 N3; theoretical value: C, 89.60; H, 4.60; N, 5.80; test value: C, 89.65; H, 4.66; N, 5.71. LC-MS: measured value: 724.05 ([M+H] + ), exact mass: 723.27.

[0201] Example 25: Synthesis of Compound 447

[0202]

[0203] Compound 447 was prepared according to the synthetic method of compound 2 in Example 1, except that intermediate F23 was used to replace intermediate F1, and raw material H6 was used to replace raw material H1. Elemental analysis: C 57 H 36 N2; theoretical value: C, 91.41; H, 4.85; N, 3.74; test value: C, 91.47; H, 4.92; N, 3.62. LC-MS: measured value: 749.46 ([M+H] + ), exact mass: 748.29.

[0204] Example 26: Synthesis of Compound 547

[0205]

[0206] Compound 547 was prepared according to the synthetic method of compound 2 in Example 1, except that intermediate F23 was used to replace intermediate F1, and raw material H8 was used to replace raw material H1. Elemental analysis: C 54 H 33N3; theoretical value: C, 89.60; H, 4.60; N, 5.80; test value: C, 89.69; H, 4.68; N, 5.63. LC-MS: Found: 724.18 ([M+H] + ), exact mass: 723.27.

[0207] Example 27: Synthesis of Compound 567

[0208]

[0209] Compound 567 was prepared according to the synthesis method of compound 2 in Example 1, except that intermediate F15 was used to replace intermediate F1. Elemental analysis: C 52 H 33 N3; theoretical value: C, 89.24; H, 4.75; N, 6.00; test value: C, 89.21; H, 4.73; N, 6.08. LC-MS: measured value: 700.06 ([M+H] + ), exact mass: 699.27.

[0210] Example 28: Synthesis of Compound 571

[0211]

[0212] Compound 571 was prepared according to the synthesis method of compound 2 in Example 1, except that intermediate F23 was used to replace intermediate F1. Elemental analysis: C 53 H 34 N2; theoretical value: C, 91.09; H, 4.90; N, 4.01; test value: C, 91.06; H, 4.98; N, 3.95. LC-MS: found value: 699.31 ([M+H] + ), exact mass: 698.27.

[0213] II. Device Preparation Example

[0214] The following describes in detail the application effect of the compound synthesized according to the present invention as a hole blocking layer material in the device through device examples 1-28 and device comparative examples 1-18. Compared with device comparative examples 1-18, device examples 1-28 have the same manufacturing process of the device, and use the same substrate material and electrode material, and the film thickness of the electrode material is also consistent. The difference is that the hole blocking layer material in the device has changed. The device layer structure is shown in Table 2, and the performance test results of each device are shown in Table 3.

[0215] The molecular structure formula of the relevant materials is shown below:

[0216]

[0217]

[0218] The structures of comparative compounds HB-1 to HB-18 are shown above. The above materials were all purchased commercially.

[0219] Device Comparison Example 1

[0220] The specific preparation process is as follows:

[0221] like Figure 1 As shown, the transparent substrate layer 1 is transparent glass, and Ag (100nm) is evaporated as the anode layer 2. On the anode layer 2, a vacuum evaporation device is used to evaporate HT-1 and P-1 with a film thickness of 10nm as the hole injection layer 3, and the mass ratio of HT-1 and P-1 is 97:3. Then, HT-1 with a thickness of 130nm is evaporated as the hole transport layer 4. Then, EB-1 with a thickness of 5nm is evaporated as the electron blocking layer 5. After the above-mentioned electron blocking material is evaporated, the light-emitting layer 6 of the OLED light-emitting device is prepared, using BH-1 as the main material and BD-1 as the doping material. The doping ratio of the doping material is 3% by weight, and the film thickness of the light-emitting layer 6 is 20nm. After the above-mentioned light-emitting layer 6, HB-1 is continuously evaporated, and the film thickness is 5nm, as a hole blocking layer 7. On 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 this material is 30nm, and this layer is the electron transport layer 8. On the electron transport layer 8, a LiF layer with a film thickness of 1nm 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 16nm 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, 65nm of CP-1 is vacuum-deposited as the light extraction layer 11 (the light extraction layer 11 is also called the CPL layer).

[0222] Device Examples 2 to 28 and Device Comparative Examples 1 to 18 were prepared in a similar manner to Device Comparative Example 1, except that the hole blocking layer 7 materials in Table 2 below were used.

[0223] Table 2

[0224]

[0225]

[0226]

[0227] III. Device Testing Example

[0228] The device prepared in II was tested for its current efficiency, CIEy and LT95 life. The current efficiency and CIEy were tested using an IVL (current-voltage-luminance) test system (Suzhou Fushida Scientific Instrument Co., Ltd.) at a current density of 10 mA / cm 2 LT95 refers to the time it takes for the device brightness to decay to 95% of the initial brightness. The current density during the test is 30mA / cm 2 ; The life test system is the EAS-62C OLED device life tester produced by Japan System Engineering Co., Ltd.; The test results are shown in Table 3 below.

[0229] Table 3

[0230]

[0231]

[0232] It can be seen from the device test data results in Table 3 above that compared with the comparative devices using HB-1, HB-2, HB-3, HB-4, HB-5, HB-6, HB-7, HB-8, HB-9, HB-10, HB-11, HB-12, HB-13, HB-14, HB-15, HB-16, HB-17, and HB-18 as hole blocking layer materials, the current efficiency of the device prepared using the compound of the present invention as the hole blocking layer material is improved and the device life is extended. For example, its life is basically more than 1.1 times that of the comparative devices 1-18, and some embodiments (such as Example 1 prepared by compound 2 of the present invention) is even more than 1.25 times that of the comparative devices 1-18.

[0233] The structural formulas of the comparative compounds HB-1 to HB-18 used in the comparative examples are close to those of the present invention, for example, only the intermediate special bridging groups, triazine substituents, and spirofluorene substituents between azabenzene and spirofluorene are different; that is, the intermediate special bridging groups, triazine or pyrimidine substituents, and spirofluorene substituents between triazine or pyrimidine and spirofluorene are different; wherein the intermediate special bridging refers to the connection of triazine or pyrimidine and spirofluorene to the ortho-phenyl group having a substituent. However, the compounds of the present invention have achieved better technical effects as hole blocking layer materials than the comparative compounds.

[0234] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

[0235] 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. A compound containing nitrogen-containing heterobenzene and spirofluorene structures, characterized in that: The compound containing nitrogen-containing heterobenzene and spirofluorene structures is shown in general formula (1): In the general formula (1), X1, X2, and X3 are each independently CH or N; at least one of X1, X2, and X3 is N; Ar represents any one of the following groups: substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted carbazolyl; R1 represents any one of the following groups: substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted pyridyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothienyl; Ar and R1 are the same or different; * indicates the connection position; R represents the structure shown in general formula (2); Ring B is represented by a substituted or unsubstituted phenyl group, or a substituted or unsubstituted naphthyl group; any unsubstituted carbon on the benzene ring or naphthalene ring in the general formula (2) can serve as a connection site with the general formula (1); The substituent of the substituted group is a deuterium atom, a cyano group, a phenyl group, a biphenyl group, a naphthyl group, a pyridyl group, a pyrimidyl group or a pyridazinyl group.

2. The compound containing nitrogen-containing heterobenzene and spirofluorene structure according to claim 1, characterized in that: The nitrogen-containing heterobenzene and spirofluorene structure compound is represented by any one of the general formulas (2-1) to (2-6): In the general formulae (2-1) to (2-6), X1, X2, X3, Ar, R1 and ring B have the same meanings as in the general formula (1).

3. The compound containing nitrogen-containing heterobenzene and spirofluorene structure according to claim 1, characterized in that: The general formula (2) is represented by any one of the general formulas a, b, c and d: In the general formula a, R2 represents a hydrogen atom, a cyano group, a phenyl group, a biphenyl group, a naphthyl group, a pyridyl group, a pyrimidyl group, a pyridazinyl group or a pyrazinyl group; Preferably, the general formula (2) is represented by any one of the following structures:

4. The compound containing nitrogen-containing heterobenzene and spirofluorene structure according to claim 1, characterized in that: The general formula (2) is represented by any one of the following structures: The R2 represents a hydrogen atom, a cyano group, a phenyl group, a biphenyl group, a naphthyl group, a pyridyl group, a pyrimidyl group, a pyridazinyl group or a pyrazinyl group; In the general formula a-1, the connection site with the general formula (1) is 1, 2, 3 or 4; the connection site of R2 is 5, 6, 7, 8, 9, 10, 11 or 12; In the general formula a-2, the connection site with the general formula (1) is 5, 6, 7, 8, 9, 10, 11 or 12; the connection site of R2 is 5, 6, 7, 8, 9, 10, 11 or 12; In the general formula b-1, the connection site with the general formula (1) is 1', 2', 3' or 4'; In the general formula b-2, the connection site with the general formula (1) is 5', 6', 7', 8', 9', 10', 11', 12', 13' or 14'; In the general formula c-1, the connection site with the general formula (1) is 1", 2", 3" or 4"; In the general formula c-2, the connection site with the general formula (1) is 5", 6", 7", 8", 9", 10", 11", 12", 13" or 14"; In the general formula d-1, the connection site with the general formula (1) is 1"', 2"', 3"' or 4"'; In the general formula d-2, the connection site with the general formula (1) is 5'", 6'", 7'", 8'", 9'", 10'", 11'", 12'", 13'" or 14'".

5. The compound containing nitrogen-containing heterobenzene and spirofluorene structure according to claim 1, characterized in that: In the general formula (1), at least two of X1, X2, and X3 are represented by N.

6. The compound containing nitrogen heterobenzene and spirofluorene structure according to claim 1, characterized in that: The Ar is selected from the following structures: Any of; The R1 is selected from the following structures: Any one of.

7. The compound containing nitrogen-containing heterobenzene and spirofluorene structure according to claim 1, characterized in that: The compound containing nitrogen-containing heterobenzene and spirofluorene structures is any one of the following structures:

8. An organic electroluminescent device comprising a substrate, a first electrode and a second electrode, wherein a plurality of organic thin film layers are provided between the first electrode and the second electrode, wherein: The organic thin film layer contains the nitrogen-containing heterobenzene and spirofluorene structure compound according to any one of claims 1 to 7. Preferably, the organic thin film layer comprises a hole transport region thin film layer, a light emitting region thin film layer and an electron transport region thin film layer, and the electron transport region thin film layer contains the nitrogen-containing heterobenzene and spirofluorene structure compounds. Preferably, the electron transport region thin film layer comprises a hole blocking layer, and the hole blocking layer contains the nitrogen-containing heterobenzene and spirofluorene structured compound.

9. The organic electroluminescent device according to claim 8, characterized in that: The hole transport region thin film layer comprises a hole injection layer, a hole transport layer and an electron blocking layer, the electron transport region thin film layer comprises a hole blocking layer, an electron transport layer and an electron injection layer, and the hole blocking layer contains the nitrogen-containing heterobenzene and spirofluorene structure compounds.

10. A display element, characterized in that: The display element comprises the organic electroluminescent device according to any one of claims 8 to 9.

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