Aromatic amine organic compound and its application

Abstract

The present invention discloses an aromatic amine organic compound and its application. The structure of the aromatic amine organic compound is shown in the general formula (1): the compound of the present invention is a monoamine compound containing benzo[4,5]imidazo[1,2-a]pyridine and its derivatives and benzoxazolyl or benzothiazolyl, has a more suitable Eg energy level and thermal stability, a lower evaporation temperature and a decomposition temperature higher than the evaporation temperature, and a higher extinction coefficient at a wavelength of 380nm, and can effectively absorb high-energy external light sources in the ultraviolet region to minimize damage to organic materials inside organic light-emitting devices. The compound of the present invention has a higher refractive index in the visible light field. After being applied to an OLED device as a covering layer, it can effectively improve the light extraction efficiency of the OLED device and reduce the angle dependence, thereby improving the device luminous efficiency and optimizing the visual deviation performance.

Description

Technical Field

[0001] The present invention relates to the field of semiconductor technology, and in particular to an aromatic amine organic compound and an application thereof as a covering layer of an organic electroluminescent device. Background Art

[0002] Organic Light Emitting Diode (OLED), also known as organic electroluminescent device, is a technology that causes organic materials to emit light through carrier injection and recombination under the action of an electric field. It can convert electrical energy into light energy through organic light-emitting materials, including passive drive OLED (PMOLED) and active drive OLED (AMOLED). OLED is a new generation of display technology after cathode ray tube (Cathode Ray Tube, CRT) and liquid crystal display (Liquid Crystal Display, LCD), and is known as a fantastic display technology. The essence of OLED is a thin film stacking device. In theory, when both the anode and the cathode are transparent electrodes, the light emitted by the light-emitting layer can be transmitted from the anode to the outside of the device and from the cathode to the outside of the device. Therefore, according to the different paths of light transmission, the device can be divided into bottom-emitting devices and top-emitting devices.

[0003] The light of the bottom-emitting device is transmitted from the anode to the outside of the device through the substrate, while the light of the top-emitting device is transmitted to the outside of the device through the cathode. The two devices have different application methods due to their different light emission methods. If a bottom-emitting device is used in an active matrix structure, its light emission path is organic layer-anode-TFT-substrate. TFT is a mesh array switch deposited on the substrate. Due to the presence of TFT, the aperture ratio of the device is further reduced. When the emitted light propagates here, it will be reflected, scattered, etc. and blocked and cannot be transmitted to the outside of the device, which seriously affects the display effect of the device. The light emission direction of the top-emitting device is on the cathode side, and it does not need to pass through the substrate. Therefore, it also avoids the TFT structure, successfully avoiding the problem of reduced aperture ratio in bottom-emitting devices, making the image more delicate and clear, and the color vividness is also higher.

[0004] In the top-emitting organic electroluminescent device structure, because the metal cathode layer and the metal reflective layer at the bottom form a resonant cavity (also called a microcavity), there is constructive interference and destructive interference. As the viewing angle changes, the distance between the metal cathode layer and the metal reflective layer at the bottom (i.e., the cavity length of the microcavity) changes accordingly, which will lead to great differences in brightness and color observed at different viewing angles, seriously affecting product performance.

[0005] In such a light-emitting element, when the light emitted from the light-emitting layer enters other films, if the light enters at an angle above a certain angle, total reflection will occur at the interface between the light-emitting layer and the other films. Therefore, only a part of the emitted light can be used. In recent years, in order to improve the light extraction efficiency and improve the color deviation, a light-emitting element with a "covering layer" with a high refractive index arranged outside a semi-transparent electrode with a low refractive index has been proposed.

[0006] Although it is proposed to use a high-precision metal mask in the formation of the cover layer, there are the following problems with the metal mask: if the temperature of the cover layer evaporation is too high, the deformation caused by heat will deteriorate the positioning accuracy. If it is a high-precision mask, it cannot be evaporated at the correct position. The evaporation temperature of many inorganic substances is high and is not suitable for the use of high-precision masks, which may also cause damage to the light-emitting element itself. Furthermore, for film formation using the sputtering method, since it causes damage to the light-emitting element, a cover layer made of inorganic substances cannot be used.

[0007] For the high-energy plasma or ultraviolet rays that the device is exposed to in the subsequent packaging, a class of stable materials is needed to avoid damage to the internal materials of the electroluminescent device. LiF is currently used more frequently. The chemical activity of the protective layer LiF is relatively high, and the TFE encapsulation layer is generally prepared by CVD process. A large amount of high-energy plasma will be generated during the preparation process, thereby releasing a large amount of energy and electrons to the internal layer structure of the device. The energy released by the high-energy plasma will cause the organic material of the covering layer to interact with the LiF of the adjacent layer, resulting in black spots on the device. In addition, the layer closest to the protective layer in the encapsulation layer may also participate in the interaction and produce black spots.

[0008] The current use of cover layers to improve the performance of OLED devices mainly has the following problems:

[0009] 1. The evaporation temperature is too high, and the CPL material decomposes seriously after long-term evaporation.

[0010] 2. The light extraction efficiency is low. After being applied to OLED devices, the device luminous efficiency is only improved to a limited extent.

[0011] 3. After being applied to OLED devices, the color deviation of the device is not significantly improved, and the angle dependence of the emitted light is strong. As the angle changes, the brightness decays, accompanied by changes in the luminous color.

[0012] 4. The optimal evaporation film thickness range is narrow. CPL materials can only achieve optimal device performance when the film thickness range is narrow. It has high requirements for the preparation process, and the quality of the resulting device products varies greatly, with a low yield rate.

[0013] In order to continuously improve the performance of OLED devices, it is necessary not only to innovate the structure and manufacturing process of OLED devices, but also to continuously research and innovate OLED optoelectronic functional materials to create higher performance OLED functional materials. Therefore, finding suitable materials as cover layers for OLED devices to solve the above problems is a long-term need in the field. Summary of the invention

[0014] In response to the above-mentioned problems existing in the prior art, the present application provides an aromatic amine organic compound. The compound of the present invention has a higher visible light refractive index and a higher extinction coefficient @380nm, a lower evaporation temperature and a higher decomposition temperature, and can be used as a covering layer to improve light extraction efficiency and improve angle dependence.

[0015] The present invention provides the following technical solutions:

[0016] An aromatic amine organic compound for an organic electroluminescent device, wherein the structure of the aromatic amine organic compound is shown in general formula (1):

[0017]

[0018] In the general formula (1), X represents O or S; m represents 1 or 2; R1 and R2 each independently represent a hydrogen atom or a phenyl group;

[0019] When R1 and R2 are independently represented by phenyl, the phenyl is connected to the main structure in a ring through a CM1-CM2 bond, a CM2-CM3 bond, a CM3-CM4 bond, a CM5-CM6 bond, a CM6-CM7 bond or a CM7-CM8 bond;

[0020] L and L1 are independently a single bond, a substituted or unsubstituted C 6-50 Arylene, substituted or unsubstituted C containing one or more heteroatoms 3-50 A heteroarylene group;

[0021] Ar1 represents a substituted or unsubstituted C 6-50 Aryl, substituted or unsubstituted C 3-50 One of the heteroaryl groups;

[0022] The substituents for the substituent groups are selected from the group consisting of a protium atom, a deuterium atom, a tritium atom, a halogen, a cyano group, a C 6-30 Aryl, C containing one or more heteroatoms 3-30 one or more of heteroaryl groups;

[0023] The heteroatom is selected from one or more of an oxygen atom, a sulfur atom and a nitrogen atom.

[0024] In a preferred embodiment, the structure of the aromatic amine organic compound is shown in any one of the general formulas (3) to (9);

[0025]

[0026]

[0027] The definitions of X, L, L1 and Ar1 are the same as those defined above.

[0028] In a preferred embodiment, the structure of the aromatic amine organic compound is shown in any one of the general formulas (10) to (15);

[0029]

[0030] The definitions of X, L, L1 and Ar1 are the same as those defined above.

[0031] In a preferred embodiment, the structure of the aromatic amine organic compound is as shown in general formula (16) or general formula (17);

[0032]

[0033] The X1 is represented by -O- or -S-; the definitions of X, L, and L1 are the same as those defined above.

[0034] More preferably, L and L1 independently represent one or more of a single bond, a phenylene group, a biphenylene group, and a naphthylene group;

[0035] The Ar1 is represented by substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted triphenylene, substituted or unsubstituted pyridyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted furyl, substituted or unsubstituted naphthobenzofuranyl, substituted or unsubstituted thienyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted N-phenylcarbazolyl, substituted or unsubstituted N-diphenylcarbazolyl, substituted or unsubstituted N-naphthylcarbazolyl, substituted or unsubstituted N-dibenzofuranylcarbazolyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted quinazoline, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted cinnolinyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted carbazoline, substituted or unsubstituted naphthyridinyl, substituted or unsubstituted benzoxazolyl, substituted or unsubstituted benzothiazolyl, substituted or unsubstituted naphthofuranyl, substituted or unsubstituted naphthothiophenyl, substituted or unsubstituted benzo[4,5]imidazo[1,2-a]pyridinyl;

[0036] The substituents for the substituent group are optionally selected from one or more of phenyl, naphthyl, biphenyl, terphenyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, quinolyl, isoquinolyl, benzoxazolyl, benzothiazolyl, benzimidazolyl, quinoxalinyl, quinazolinyl, cinnolinyl, naphthyridinyl, fluorenyl, dibenzofuranyl, N-phenylcarbazolyl, dibenzothiophenyl, naphthofuranyl and naphthothiophenyl.

[0037] In a preferred embodiment, the specific structure of the aromatic amine organic compound is any one of the following structures:

[0038]

[0039]

[0040]

[0041]

[0042]

[0043]

[0044]

[0045]

[0046]

[0047]

[0048]

[0049] Further preferably, the extinction coefficient of the aromatic amine organic compound at a wavelength of 380nm is 0.8-1.3; the refractive index under blue light with a wavelength of 450nm is 2.33-2.40, preferably 2.35-2.40; the refractive index under green light with a wavelength of 525nm is 2.15-2.23; the refractive index under red light with a wavelength of 620nm is 2.10-2.15, preferably 2.12-2.15; and the difference in refractive index under blue light and red light is 0.20-0.27, preferably 0.20-0.26, most preferably 0.22-0.26; the evaporation temperature of the aromatic amine organic compound is lower than the decomposition temperature, and the evaporation temperature is 300-360℃, preferably 300-350℃, and more preferably 330-350℃.

[0050] An organic electroluminescent device comprises: a substrate layer; a first electrode, which is on the substrate; an organic light-emitting functional layer, which is on the first electrode; a second electrode, which is on the organic light-emitting functional layer; and a covering layer, which is on the second electrode; the covering layer contains the aromatic amine organic compound.

[0051] Further preferably, the thickness of the covering layer is 10-1000 nm, preferably 40-140 nm, more preferably 50-90 nm, more preferably 60 nm-80 nm, most preferably 65-75 nm.

[0052] More preferably, the organic electroluminescent device comprises one or more combinations of blue, green or red organic light-emitting material layers; different organic light-emitting material layers are stacked in a transverse or longitudinal manner.

[0053] The beneficial effects of the present invention are:

[0054] The compound represented by the general formula (1) of the present invention has excellent properties. Compared with CP-1, CP-2 and CP-3, it has a higher visible light refractive index and a suitable difference between the refractive index under blue light and red light. The refractive index of the aromatic amine organic compound of the present invention is in the range of 2.35-2.40 under blue light with a wavelength of 450nm; in the range of 2.17-2.23 under green light with a wavelength of 525nm; and in the range of 2.10-2.16 under red light with a wavelength of 620nm. This is conducive to improving the light extraction effect of the device and improving the visual deviation effect.

[0055] The compound represented by the general formula (1) of the present invention also has a relatively low evaporation temperature of 300-360°C, preferably 300-350°C, more preferably 330-350°C, which is lower than the decomposition temperature to ensure that it will not decompose during the evaporation process and has high thermal stability.

[0056] The compound represented by the general formula (1) of the present invention has an extinction coefficient in the range of 0.8-1.3 at a wavelength of 380 nm, and can effectively absorb high-energy external light sources in the ultraviolet region to minimize damage to organic materials inside the organic light-emitting device, thereby helping to significantly improve the stability and service life of the organic light-emitting device.

[0057] The compound of the present invention is a monoamine organic compound containing benzo[4,5]imidazo[1,2-a]pyridine and its derivatives and benzoxazolyl or benzothiazolyl, having a high glass transition temperature and molecular thermal stability, requiring a low temperature for vapor deposition, and the decomposition temperature of the material is greater than the vapor deposition temperature of the material, thus effectively avoiding decomposition during vapor deposition and being suitable for long-term vapor deposition, while ensuring that the material will not crystallize after film formation. In addition, it has a high visible light refractive index in the visible light field, and after being applied to OLED devices as a covering layer with a suitable Eg energy level, it can effectively improve the light extraction efficiency of OLED devices, reduce device power consumption, and improve the device's visual deviation and the angular dependence of the emitted light, expand the optimal vapor deposition film thickness range under the premise of ensuring the best device performance, and effectively improve the yield rate of flexible TFE packaging devices containing a LiF protective layer.

[0058] The compound of the present invention is suitable for long-term evaporation. After being applied to light-related devices, it can improve the light extraction efficiency of the device and improve the angle dependence of the emitted light, and has a larger optimal evaporation film thickness range under the premise of ensuring the best device performance, thereby reducing the requirements for the preparation process and effectively improving the yield rate of flexible TFE packaged devices. Therefore, the compound of the present invention is particularly suitable for use in light-related devices or components, wherein, in particular, the compound of the present invention can be used as a covering layer in the device or component to improve the light extraction efficiency and improve the angle dependence. In addition, using the compound of the present invention as a covering layer to prepare a device or component can expand the optimal evaporation film thickness range and improve the yield rate of flexible TFE packaged devices. BRIEF DESCRIPTION OF THE DRAWINGS

[0059] Figure 1 is a schematic cross-sectional structure diagram of an application example (top-emitting organic electroluminescent device) of the compound of the present invention,

[0060] Among them, 100 is a substrate, 200 is a first electrode, 300 is an organic light-emitting functional layer, 400 is a second electrode, and 500 is a covering layer.

[0061] Figure 2 for Figure 1 Schematic diagram of the cross-sectional structure of the organic light-emitting functional layer 300 of the top-emitting organic electroluminescent device, wherein 310 (HIL) is a hole injection layer, 320 (HTL) is a hole transport layer, 330 (EBL) is an electron blocking layer, 340 (EML) is a light-emitting layer, 350 (HBL) is a hole blocking layer, 360 (ETL) is an electron transport layer, and 370 (EIL) is an electron injection layer.

[0062] Figure 3 A structure of the light-emitting layer 340 is formed by composite light-emitting material layers stacked together vertically, wherein EM1, EM2, and EM3 are respectively a blue organic light-emitting material layer, a green organic light-emitting material layer, and a red organic light-emitting material layer, in no particular order.

[0063] Figure 4 The light-emitting layer 340 is constructed in such a way that it is formed by laterally arranged composite light-emitting material layers, wherein EM1, EM2, and EM3 are respectively a blue organic light-emitting material layer, a green organic light-emitting material layer, and a red organic light-emitting material layer, in no particular order. DETAILED DESCRIPTION

[0064] Throughout the specification, unless explicitly described to the contrary, "comprising" any component will be understood to imply the inclusion of other elements, rather than excluding any other elements. In addition, it should be understood that throughout the specification, when an element such as a layer, film, region or substrate is referred to as being "on" or "above" another element, it can be "directly on" another element, or there may be intervening elements. In addition, "on..." or "above..." means being located above the target portion, and does not necessarily mean being located above according to the direction of gravity.

[0065] In this article, "n@450nm" used refers to the refractive index of the material relative to vacuum for blue light with a wavelength of 450nm; "n@525nm" refers to the refractive index of the material relative to vacuum for green light with a wavelength of 525nm; "n@620nm" refers to the refractive index of the material relative to vacuum for red light with a wavelength of 620nm; "k@380nm" refers to the extinction coefficient of the material relative to vacuum for a wavelength of 380nm.

[0066] In this paper, the C 6-50 The aryl group refers to a monovalent group including a carbocyclic aromatic system having 6 to 50 carbon atoms as ring atoms. 6-50 Non-limiting examples of aryl groups may include phenyl, biphenyl, phenanthrenyl, terphenyl, naphthyl, phenanthrenyl, triphenylenyl, and the like. 6-50 When the aryl group includes two or more rings, these rings may be fused to each other.

[0067] In this paper, the C 3-50 The heteroaryl group refers to a monovalent group including a carbocyclic aromatic system having at least one heteroatom selected from N, O, P and S as a ring-forming atom and 3 to 50 carbon atoms. 3-50 Non-limiting examples of heteroaryl groups may include pyridyl, oxadiazolyl, triazinyl, pyrimidinyl, furanyl, dibenzofuranyl, dibenzothiophenyl, benzoxazolyl, bisbenzoxazolyl, carbazolyl, N-phenylcarbazolyl, quinolyl, isoquinolyl, naphthofuranyl, phenyl-substituted naphthofuranyl, and the like. 3-50 When the heteroaryl group includes two or more rings, these rings may be fused to each other.

[0068] In this paper, the C 6-30 The aryl group refers to a monovalent group including a carbocyclic aromatic system having 6 to 30 carbon atoms as ring atoms. 6-30 Non-limiting examples of the aryl group may include phenyl, biphenyl, phenanthrenyl, terphenyl, naphthyl, phenanthrenyl, triphenylenyl, and the like.

[0069] In this paper, the C 3-30 The heteroaryl group refers to a monovalent group including a carbocyclic aromatic system having at least one heteroatom selected from N, O, P and S as a ring-forming atom and 3 to 30 carbon atoms. 3-30 Non-limiting examples of heteroaryl groups can include pyridyl, oxadiazolyl, triazinyl, pyrimidinyl, furanyl, dibenzofuranyl, dibenzothiophenyl, benzoxazolyl, bisbenzoxazolyl, carbazolyl, N-phenylcarbazolyl, quinolyl, isoquinolyl, naphthofuranyl, phenyl-substituted naphthofuranyl, and the like.

[0070] Organic electroluminescent devices

[0071] The compounds of the present invention are particularly suitable for evaporation and for improving light extraction efficiency, and can improve the stability of the production process, increase the optimal evaporation film thickness range, and avoid the device black spot phenomenon, etc. The obtained device or element has a high yield and a high visible light extraction efficiency. Therefore, an object of the present invention is to provide an organic electroluminescent device, which includes: a substrate layer; a first electrode, the first electrode is on the substrate; an organic light-emitting functional layer, the organic light-emitting functional layer is on the first electrode; a second electrode, the second electrode is on the organic light-emitting functional layer; and a covering layer, the covering layer is on the second electrode; wherein the covering layer includes one or more components of the compound described in general formula (1).

[0072] In one embodiment of the present invention, the covering layer in the organic electroluminescent (OLED) device comprises one or more of the compounds of the above-mentioned general formula (1) or consists of one or more compounds of the above-mentioned general formula (1); wherein the covering layer is 10-1000nm, preferably 40-140nm, more preferably 50-90nm, more preferably 60-80nm, and most preferably 65-75nm.

[0073] In a preferred embodiment, the device comprises one or more combinations of blue, green or red organic light-emitting material layers; different organic light-emitting material layers are stacked in combination horizontally or vertically.

[0074] In a preferred embodiment of the present invention, an OLED is provided, which includes a substrate, an anode, a cathode, an organic light-emitting functional layer and a covering layer, wherein the organic light-emitting functional layer may include a light-emitting layer, a hole transport layer, a hole injection layer, an electron blocking layer, an electron transport layer, an electron injection layer, etc., or may only include a light-emitting layer and one or more other layers, wherein the covering layer is composed of one or more of the compounds of the above general formula (1) or includes one or more compounds of the general formula (1). Optionally, there is a protective layer and an encapsulation layer on the covering layer.

[0075] like Figure 1 As shown, the substrate 100 can be any substrate used in a typical organic light-emitting device. It can be a glass or transparent plastic substrate, or a substrate made of an opaque material such as silicon or stainless steel, or a flexible PI film. Different substrates have different mechanical strengths, thermal stability, transparency, surface smoothness, and waterproofness. Depending on the properties of the substrate, the use direction is different.

[0076] A first electrode 200 is formed on the substrate 100. The first electrode 200 may be a cathode or an anode. Here, the first electrode 200 may be a reflective electrode such as a reflective film formed of silver (Ag), magnesium (Mg), aluminum (Al), gold (Au), nickel (Ni), chromium (Cr)) or an alloy thereof, or an electrode formed by a combination of a reflective film and a transparent or semi-transparent electrode, such as a transparent or semi-transparent electrode layer having a high work function and formed on the reflective film. The transparent or semi-transparent electrode layer may be formed of indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO), aluminum zinc oxide (AZO), indium gallium oxide (IGO), indium oxide (In2O3) or tin oxide (SnO2); or may be formed by a combination of metal and oxide, such as ITO / Ag / ITO, IGO / Al / IGO or AZO / Ag / AZO.

[0077] The first electrode 200 may be formed by sputtering, ion plating, vacuum evaporation, spin coating, electron beam evaporation, or chemical vapor deposition (CVD), and is preferably formed by sputtering.

[0078] The thickness of the first electrode layer 200 depends on the material used, and is generally 5 nm-1 μm, preferably 10 nm-1 μm, more preferably 10 nm-500 nm, particularly preferably 10 nm-300 nm, and most preferably 10 nm-200 nm.

[0079] like Figure 2 As shown, the organic light-emitting functional layer 300 may include a light-emitting layer 340 (EML), and if the first electrode 200 is an anode, a hole transport region may be formed between the EML and the first electrode 200, and an electron transport region may be formed between the EML and the second electrode layer 400; if the first electrode 200 is a cathode, an electron transport region may be formed between the EML and the first electrode 200, and a hole transport region may be formed between the EML and the second electrode layer 400. The hole transport region may include at least one of a hole injection layer 310 (HIL), a hole transport layer 320 (HTL), and an electron blocking layer 330 (EBL). The electron transport region may include at least one of a hole blocking layer 350 (HBL), an electron transport layer 360 (ETL), and an electron injection layer 370 (EIL). Therefore, the organic light-emitting functional layer 300 includes a light-emitting layer and a combination of at least two layers of a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer, and an electron injection layer.

[0080] The thickness of the organic light-emitting functional layer 300 is 50 nm-1000 nm.

[0081] As materials for the hole injection layer, the hole transport layer, and the electron blocking layer (HIL310, HTL320, EBL330), any material may be selected from known related materials used for OLED devices.

[0082] At least one layer of the HIL 310 and the HTL 320 may further include a charge generating material for improving conductivity. The charge generating material may be a p-dopant. Non-limiting compounds of the p-dopant are: quinone derivatives, such as tetracyanoquinodimethane (TCNQ) and 2,3,5,6-tetrafluoro-tetracyano-1,4-benzoquinodimethane (F4-TCNQ); or hexaazatriphenylene derivatives, such as 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HAT-CN); or cyclopropane derivatives, such as 4,4',4"-((1E,1'E,1"E)-cyclopropane-1,2,3-trimethylenetris(cyanoformyl))tris(2,3,5,6-tetrafluorobenzyl); or metal oxides, such as tungsten oxide and molybdenum oxide, but are not limited thereto.

[0083] The triplet state (T1) energy level of the EBL330 material is required to be higher than the T1 energy level of the main material in the light-emitting layer 340, which can play a role in blocking the energy loss of the light-emitting layer material; the HOMO energy level of the EBL330 material is between the HOMO energy level of the HTL320 material and the HOMO energy level of the main material of the light-emitting layer 340, which is conducive to the injection of holes from the positive electrode into the light-emitting layer. At the same time, the EBL330 material is required to have a high hole mobility, which is conducive to hole transmission and reduces the application power of the device; the LUMO energy level of the EBL330 material is higher than the LUMO energy level of the main material of the light-emitting layer 340, which plays a role in electron blocking, that is, the EBL330 material is required to have a wide bandgap width (Eg). The EBL330 material that meets the above conditions can be a triarylamine derivative, a fluorene derivative, a spirofluorene derivative, a dibenzofuran derivative, a carbazole derivative, 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.

[0084] In order to obtain a high-efficiency OLED device, the light-emitting layer 340 can use the same doping material or multiple doping materials. The doping material can be a simple fluorescent material, a delayed fluorescent (TADF) material or a phosphorescent material, or a combination of different fluorescent materials, TADF materials, and phosphorescent materials. The light-emitting layer 340 can be a single light-emitting layer material or a composite light-emitting layer material stacked together horizontally or vertically. The light-emitting layer 340 constituting the above-mentioned OLED light emitter can be selected from the following multiple structures:

[0085] (1) Single organic light-emitting layer material;

[0086] (2) Any combination of blue organic light-emitting layer materials and green, yellow or red light-emitting layer materials, regardless of the order;

[0087] (3) Any combination of blue organic light-emitting layer materials and green, yellow or red light-emitting layer materials, in no particular order, such as Figure 3 As shown;

[0088] (4) The blue organic light-emitting layer material, the green organic light-emitting layer material, and the red organic light-emitting layer material are arranged horizontally, such as Figure 4 shown.

[0089] In order to adjust the effective combination of carrier charges in the light-emitting layer, the film thickness of the light-emitting layer 340 constituting the OLED light-emitting body can be adjusted arbitrarily as needed, or light-emitting layers of different colors can be alternately superimposed and combined as needed, and charge blocking layers with different functional purposes can be added to the organic layer adjacent to the light-emitting layer.

[0090] The host material constituting the light-emitting layer of the above-mentioned OLED light-emitting body needs to have not only bipolar charge transfer characteristics, but also an appropriate energy level, so that the excitation energy generated by the recombination of electrons and holes can be effectively transferred to the guest light-emitting material, that is, the doping material. Such materials include, for example, distyryl arylene derivatives, isocyanate derivatives, carbazole derivatives, triarylamine derivatives, anthracene derivatives, pyrene derivatives, triazine derivatives, xanthone derivatives, triphenylene derivatives, triazine derivatives, hexaphenylene derivatives or bis(2-methyl-8-quinoline)(p-phenylphenol)aluminum (BAlq).

[0091] The materials constituting the hole blocking layer 350 and the electron transport layer 360 of the OLED device can be any materials selected from materials used for OLEDs that have electron transport properties. Examples of such materials include oxadiazole derivatives such as 1,3-bis[5'-(p-tert-butylphenyl)-1,3,4-oxadiazole-2'-yl]benzene, 2-(4-biphenyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole, triazole derivatives such as 3-(4'-tert-butylphenyl)-4-phenyl-5-(4"-biphenyl)-1,2,4-triazole, triazine derivatives, quinoline derivatives, quinoxaline derivatives, diphenylquinone derivatives, nitro-substituted quinone derivatives, thiopyran dioxide derivatives, anthraquinone dimethane derivatives, thiopyran dioxide derivatives, heterocyclic tetracarboxylic anhydrides such as naphthyl perylene, carbodiimides, quinone derivatives, anthraquinone dimethane derivatives, anthrone derivatives, distyrylpyrazine derivatives, silpentadiene derivatives, phenanthroline derivatives or imidazopyridine derivatives.

[0092] A second electrode 400 is formed on the organic light-emitting functional layer 300. The second electrode layer can be a cathode or an anode, and can be a transparent electrode or a semi-transparent electrode. The second electrode 400 can be made of a thin film with a low work function made of lithium, calcium, lithium fluoride / calcium, lithium fluoride / aluminum, aluminum, silver, magnesium or an alloy thereof. Further, the second electrode layer 400 can be made of an alloy including silver and at least one metal, wherein the at least one metal includes aluminum, platinum, ytterbium, chromium or magnesium. Moreover, the weight ratio of Ag in the alloy can be the same as that of other metals or greater than or less than the weight of other metals. For example: the second electrode layer 400 can be formed of an Ag-Mg alloy, wherein the mass ratio of Ag to Mg can be 90:10 to 10:90. Alternatively, the second electrode layer 400 can be formed of an alloy including at least one metal such as silver, gold, platinum, copper, nickel or tungsten and at least one metal such as ytterbium, indium, magnesium or chromium. These metal films can form transparent or semi-transparent electrodes by adjusting the thickness of the film. Therefore, the light generated by the organic light emitting functional layer 300 can be emitted through the second electrode layer 400. In addition, the thickness of the second electrode layer 400 can be 5-20 nm.

[0093] A covering layer 500 is formed on the second electrode layer 400 . The material used for the covering layer 500 is composed of one or more compounds of the above-mentioned general formula (1) or includes one or more compounds of the general formula (1).

[0094] The covering layer of the present invention is 10-1000 nm, preferably 40-140 nm, more preferably 50-90 nm, more preferably 60-80 nm, most preferably 65-75 nm.

[0095] refer to Figure 1 The organic electroluminescent device of the present invention includes a substrate layer 100 , a first electrode layer 200 , an organic light-emitting functional layer 300 , a second electrode layer 400 and a covering layer 500 .

[0096] A barrier layer (which may be composed of inorganic materials and / or organic materials to prevent foreign matter from penetrating the substrate and the device) and a wiring layer (which may include a driving TFT, a capacitor, a wire and a low-temperature polysilicon LTPS) may be formed on the substrate layer using known methods.

[0097] In a specific embodiment, the first electrode 200 may be a reflective electrode and the second electrode 400 may be a transparent or semi-transparent electrode. Therefore, the light generated by the organic light-emitting functional layer 300 may be directly emitted from the second electrode 400, or may be reflected by the first electrode 200 toward the second electrode 400 and then emitted. The first electrode 200 may be prepared by, for example, an evaporation method or a sputtering method. The second electrode 400 may be prepared by, for example, a vacuum evaporation method.

[0098] The organic light-emitting functional layer 300 may include a light-emitting layer 340 (EML), and a hole transport region may be formed between the EML and the first electrode 200, and an electron transport region may be formed between the EML and the second electrode layer 400. The hole transport region may include at least one of a hole injection layer 310 (HIL), a hole transport layer 320 (HTL), and an electron blocking layer 330 (EBL). The electron transport region may include at least one of a hole blocking layer 350 (HBL), an electron transport layer 360 (ETL), and an electron injection layer 370 (EIL).

[0099] The organic light-emitting functional layer 300 may be composed of small molecule organic materials or polymer materials, and the organic light-emitting functional layer 300 may be prepared by various methods, such as vacuum evaporation, solution spin coating, screen printing, and inkjet printing.

[0100] The covering layer 500 may be composed of the organic compound based on the heteroarylamine structure, and the covering layer 500 may be prepared by various methods, such as vacuum evaporation, solution spin coating, screen printing, and inkjet printing.

[0101] In addition, you can refer to Figure 1 , Figure 2 The structure of the top-emitting organic electroluminescent device is prepared by Figure 3 or Figure 4 That is, the organic light-emitting devices according to the embodiments can be configured into various structures, such as a single-color light-emitting device, a multi-color light-emitting device, or a white light-emitting top-emitting organic electroluminescent device.

[0102] A protective layer is disposed on the cover layer 500. The protective layer contains lithium fluoride (LiF). The thickness of the protective layer depends on the material used, and is generally 20-400 nm, preferably 30-200 nm, and more preferably 40-100 nm.

[0103] An encapsulation layer is arranged on the protective layer. The encapsulation layer is a protective structure for preventing foreign substances such as moisture and oxygen from entering the organic layer of the organic electroluminescent device, and is a multilayer film covering the entire surface of the organic layer, the covering layer, and the protective layer. It includes a first encapsulation layer on the protective layer, a second encapsulation layer on the first encapsulation layer, and a third encapsulation layer on the second encapsulation layer; the first encapsulation layer is an inorganic layer; the second encapsulation layer is an organic layer; the third encapsulation layer is an inorganic layer; the inorganic layer contains a material selected from Al2O3, SiO x N y 、TiO2、SiO x and SiN xAt least one of the group consisting of, wherein x and y are the same or different, and x and y are independently greater than 0 and less than 10, preferably greater than 0 and less than 5, and most preferably greater than 0 and less than 3. The inorganic layer is prepared by chemical vapor deposition (CVD).

[0104] As the encapsulation layer organic material of the organic electroluminescent device of the present invention, the encapsulation layer organic material for organic electroluminescent devices known in the prior art can be used. In a preferred embodiment of the present invention, the encapsulation layer organic material used is polydimethylsiloxane (PDMS), polymethyl methacrylate (PMMA), polystyrene (PS), a polymer derivative with a phenol group, an acrylic polymer (acryl-based polymer), an imide polymer (imide-based polymer), an arylether polymer (arylether-based polymer), an amide polymer (amide-based polymer), a fluorine polymer (fluorine-based polymer), a p-xylene polymer (p-xylene-based polymer), a vinyl alcohol polymer (vinylalcohol-based polymer) or a mixture thereof.

[0105] The thickness of the encapsulation layer organic material is sufficient to cover the encapsulation inorganic layer, and the encapsulation layer organic material is cured into a polymer by UV curing.

[0106] According to the present invention, the organic electroluminescent device is preferably a top-emitting organic electroluminescent device, which comprises, after preparing an anode, a cathode and an organic light-emitting functional layer, vapor-depositing a material comprising a compound of the general formula (1) of the present invention as a covering layer on the light-emitting side to improve light extraction efficiency and visual deviation problems.

[0107] The visual deviation problem mentioned in this article refers to the gradual change in luminous color when observing the device at different angles. In this article, improving visual deviation and reducing angle dependence is reflected in the fact that the trend of luminous color change is significantly reduced as the observation angle changes, and the luminous color does not change under ideal conditions. It can be measured by the parameter JNCD (JUST NOTICEABLE COLOR DIFFERENCE). JNCD is the obvious color difference that can be perceived by the human eye. The smaller the JNCD value, the more obvious the effect of improving visual deviation.

[0108] Furthermore, the OLED devices of the present invention can be used in OLED lighting and display devices.

[0109] Preferably, the OLED device prepared by the present invention is used in the fields of smart phones, tablet computers, smart wearable devices, large-size application fields such as televisions, VR, micro-display fields, and car central control screens or car taillights.

[0110] Example

[0111] The present invention is described in detail below in conjunction with the accompanying drawings and embodiments.

[0112] I. Synthesis of Intermediate B

[0113] Synthesis of intermediate B-1:

[0114]

[0115] The raw material A-1 (0.25 mmol) was dissolved in a solution of 10 mL toluene and ethanol in a ratio of 1:1, and the raw material D-2 (0.25 mmol) and tetrakis(triphenylphosphine)palladium (0.01 mmol) and 5 mL of potassium carbonate aqueous solution (2 mmol / L) were added, and then heated under reflux for 11 hours under stirring. After the reaction solution was restored to room temperature, it was extracted with ethyl acetate (100 mL). After washing the organic layer with saturated brine, it was dehydrated with anhydrous magnesium sulfate and the solvent was removed by distillation under reduced pressure. The residue was subjected to silica gel column chromatography with ethyl acetate / hexane (1 / 4 (volume ratio)) as the elution solvent, and the intermediate B-1 was obtained in an amount of 90.0 mg (yield 55.9%). LC-MS: Measured value: 323.03 ([M+H] + ); exact mass: 322.01.

[0116] The preparation of intermediate B-6 can refer to the prior art.

[0117] Other intermediates B were prepared by a synthetic method similar to that of intermediate B-1, and the raw materials A and D used were shown in Table 1;

[0118] Table 1

[0119]

[0120] II. Synthesis of Intermediate E:

[0121] Synthesis of intermediate E-3:

[0122]

[0123] Under nitrogen protection, in a 500ml round-bottom flask, raw material D-3 (10mmol), raw material F-3 (12mmol), 200ml toluene were added in sequence and stirred and mixed. After nitrogen was passed for 30min to replace the air three times, Pd2(dba)3 (0.05mmol), P(t-Bu)3 (0.15mmol), sodium tert-butoxide (30mmol) were added, and heated under reflux for 24h under nitrogen protection. The reaction solution was taken for TCL detection to find that the intermediate D-3 reacted completely. After the reaction was completed, the reaction system was naturally cooled to room temperature, the solvent was removed by rotary evaporation, and the residue was dissolved by adding ethyl acetate (150ml), washed with water (100ml), poured into a separating funnel, shaken, and then allowed to stand for stratification. After separation, the aqueous phase was extracted with ethyl acetate (50ml*3), the organic phases were combined, dried with anhydrous magnesium sulfate, filtered, and the filtrate was evaporated to remove ethyl acetate to obtain a crude product, which was purified by silica gel chromatography to obtain intermediate E-3. LC-MS: Found: 463.33 ([M+H] + ); exact mass: 462.17.

[0124] Intermediate E was prepared by a synthetic method similar to that of intermediate E-1, and the raw materials D and F used were shown in Table 2;

[0125] Table 2

[0126]

[0127] The reactions involved in the preparation of intermediates E-1, E-2, E-7, E-8 and E-10 are conventional carbon-nitrogen coupling reactions and can be prepared by referring to the prior art.

[0128] III. Preparation of the compounds of the present invention

[0129] Example 1: Synthesis of Compound 1:

[0130]

[0131] Under nitrogen protection, in a 500ml round-bottom flask, add intermediate B-4 (10mmol), intermediate E-1 (12mmol), and 200ml toluene in sequence, stir and mix, pass nitrogen for 30min to replace the air, add Pd2(dba)3 (0.05mmol), P(t-Bu)3 (0.15mmol), sodium tert-butoxide (30mmol), and heat under reflux for 24h. Take the reaction solution TCL detection to find that the reaction of intermediate B-4 is complete. After the reaction is completed, the reaction system is naturally cooled to room temperature, the solvent is removed by rotary evaporation, and the residue is dissolved in ethyl acetate (150ml), washed with water (100ml), poured into a separatory funnel and shaken, and then allowed to stand for stratification. After separation, the aqueous phase is extracted with ethyl acetate (50ml*3), the organic phases are combined and dried with anhydrous magnesium sulfate, filtered, and the filtrate is evaporated to remove ethyl acetate to obtain a crude product, which is purified by silica gel chromatography to obtain compound 1. Elemental analysis structure (molecular formula C 43 H 27 N5O2) theoretical value: C, 79.98; H, 4.21; N, 10.85; test value: C, 79.97; H, 4.23; N, 10.84. LC-MS: Measured value: 646.42 ([M+H] + ); exact mass: 645.22.

[0132] Example 2: Synthesis of Compound 2:

[0133]

[0134] Compound 2 was prepared by referring to the synthesis method of compound 1 in Example 1, except that intermediate B-2 was used to replace intermediate B-4. Elemental analysis (C 43 H 27 N5O2) theoretical value: C, 79.98; H, 4.21; N, 10.85; test value: C, 79.99; H, 4.20; N, 10.81. LC-MS: Measured value: 646.03 ([M+H] + ); exact mass: 645.22.

[0135] Example 3: Synthesis of Compound 3:

[0136]

[0137] Compound 3 was prepared by referring to the synthesis method of compound 1 in Example 1, except that intermediate B-3 was used to replace intermediate B-4. Elemental analysis (C 43 H 27N5O2) theoretical value: C, 79.98; H, 4.21; N, 10.85; test value: C, 79.97; H, 4.23; N, 10.81. LC-MS: Measured value: 646.35 ([M+H] + ); exact mass: 645.22.

[0138] Example 4: Synthesis of Compound 17:

[0139]

[0140] Compound 17 was prepared by referring to the synthesis method of compound 1 in Example 1, except that intermediate B-6 was used to replace intermediate B-4, and intermediate E-10 was used to replace intermediate E-1. Elemental analysis (C 37 H 23 N5OS) theoretical value: C, 75.88; H, 3.96; N, 11.96; S, 5.47; test value: C, 75.85; H, 3.95; N, 11.98; S, 5.45. LC-MS: Found: 586.37 ([M+H] + ); exact mass: 585.16.

[0141] Example 5: Synthesis of Compound 27:

[0142]

[0143] Compound 27 was prepared by referring to the synthesis method of compound 1 in Example 1, except that intermediate B-5 was used to replace intermediate B-4, and intermediate E-2 was used to replace intermediate E-1. Elemental analysis (C 42 H 28 N4O) theoretical value: C, 83.42; H, 4.67; N, 9.27; test value: C, 83.41; H, 4.66; N, 9.28. LC-MS: Found: 605.09 ([M+H] + ); exact mass: 604.23.

[0144] Example 6: Synthesis of Compound 43:

[0145]

[0146] Compound 43 was prepared by referring to the synthesis method of compound 1 in Example 1, except that intermediate B-3 was used to replace intermediate B-4, and intermediate E-4 was used to replace intermediate E-1. Elemental analysis (C 46 H 30N4O) theoretical value: C, 84.38; H, 4.62; N, 8.56; test value: C, 84.39; H, 4.60; N, 8.57. LC-MS: Found: 655.14 ([M+H] + ); exact mass: 654.24.

[0147] Example 7: Synthesis of Compound 56:

[0148]

[0149] Compound 56 was prepared by referring to the synthesis method of compound 1 in Example 1, except that intermediate B-1 was used to replace intermediate B-4, and intermediate E-3 was used to replace intermediate E-1. Elemental analysis (C 50 H 32 N4O) theoretical value: C, 85.20; H, 4.58; N, 7.95; test value: C, 85.21; H, 4.57; N, 7.96. LC-MS: Found: 705.42 ([M+H] + ); exact mass: 704.26.

[0150] Example 8: Synthesis of Compound 57:

[0151]

[0152] Compound 57 was prepared by referring to the synthesis method of compound 1 in Example 1, except that intermediate E-6 was used to replace intermediate E-1. Elemental analysis (C 48 H 30 N4O) theoretical value: C, 84.93; H, 4.45; N, 8.25; test value: C, 84.94; H, 4.42; N, 8.24. LC-MS: Found: 679.34 ([M+H] + ); exact mass: 678.24.

[0153] Example 9: Synthesis of Compound 81:

[0154]

[0155] Compound 81 was prepared by referring to the synthesis method of compound 1 in Example 1, except that raw material F-9 was used to replace intermediate B-4. Elemental analysis (C 41 H 25 N5O2) theoretical value: C, 79.47; H, 4.07; N, 11.30; test value: C, 79.46; H, 4.09; N, 11.31. LC-MS: Found: 620.18 ([M+H] + ); exact mass: 619.20.

[0156] Example 10: Synthesis of Compound 165:

[0157]

[0158] Compound 165 was prepared by referring to the synthesis method of compound 1 in Example 1, except that raw material F-12 was used to replace intermediate B-4. Elemental analysis (C 41 H 25 N5O2) theoretical value: C, 79.47; H, 4.07; N, 11.30; test value: C, 79.49; H, 4.06; N, 11.31. LC-MS: Found: 620.22 ([M+H] + ); exact mass: 619.20.

[0159] Example 11: Synthesis of Compound 188:

[0160]

[0161] Compound 188 was prepared by referring to the synthesis method of compound 1 in Example 1, except that intermediate B-5 was used to replace intermediate B-4, and intermediate E-8 was used to replace intermediate E-1. Elemental analysis (C 42 H 26 N4OS) theoretical value: C, 79.47; H, 4.13; N, 8.83; S, 5.05; found value: C, 79.46; H, 4.14; N, 8.85; S, 5.03. LC-MS: found value: 635.09 ([M+H] + ); exact mass: 634.18.

[0162] Example 12: Synthesis of Compound 229:

[0163]

[0164] Compound 229 was prepared by referring to the synthesis method of compound 1 in Example 1, except that intermediate B-3 was used to replace intermediate B-4, and intermediate E-11 was used to replace intermediate E-1. Elemental analysis (C 47 H 30 N6O) theoretical value: C, 81.25; H, 4.35; N, 12.10; test value: C, 81.23; H, 4.36; N, 12.11. LC-MS: Found: 695.28 ([M+H] + ); exact mass: 694.25.

[0165] Example 13: Synthesis of Compound 232:

[0166]

[0167] Compound 232 was prepared by referring to the synthesis method of compound 1 in Example 1, except that raw material F-9 was used to replace intermediate B-4, and intermediate E-9 was used to replace intermediate E-1. Elemental analysis (C 43 H 26 N6O) theoretical value: C, 80.36; H, 4.08; N, 13.08; test value: C, 80.35; H, 4.07; N, 13.09. LC-MS: Found: 643.15 ([M+H] + ); exact mass: 642.22.

[0168] Example 14: Synthesis of Compound 245:

[0169]

[0170] Compound 245 was prepared by referring to the synthesis method of compound 1 in Example 1, except that intermediate B-3 was used to replace intermediate B-4, and intermediate E-5 was used to replace intermediate E-1. Elemental analysis (C 44 H 28 N4O) theoretical value: C, 84.06; H, 4.49; N, 8.91; test value: C, 84.05; H, 4.47; N, 8.92. LC-MS: Found: 629.26 ([M+H] + ); exact mass: 628.23.

[0171] Example 15: Synthesis of Compound 266:

[0172]

[0173] Compound 266 was prepared by referring to the synthesis method of compound 1 in Example 1, except that intermediate B-3 was used to replace intermediate B-4, and intermediate E-7 was used to replace intermediate E-1. Elemental analysis (C 48 H 30 N4O2) theoretical value: C, 82.98; H, 4.35; N, 8.06; test value: C, 82.96; H, 4.31; N, 8.08. LC-MS: Measured value: 695.22 ([M+H] + ); exact mass: 694.24.

[0174] IV Determination of physical properties of compounds

[0175] Determination method: The refractive index n and extinction coefficient k (isotropic glass substrate) are measured by ellipsometer (U.S. JA Woollam Co. model: ALPHA-SE) (tested in atmospheric environment); the band gap Eg is tested by double-beam UV-visible spectrophotometer (Beijing Puxi General Company, model: TU-1901); the heat resistance experiment is carried out on a thermal stability equipment (model BOF-800C-8D).

[0176] The compound of the present invention and comparative compounds CP-1, CP-2 and CP-3 were measured by the above determination method. All test results are shown in Tables 3 and 4 below.

[0177] Table 3

[0178]

[0179]

[0180] Table 4

[0181]

[0182] Note: The evaporation temperature is when the material is at TS (TS is the vertical distance from the evaporation substrate to the evaporation source) of 500 mm, vacuum degree <1.0E-5Pa, and evaporation rate The evaporation temperature at that time; the judgment standard for material decomposition is: HPLC before heat resistance minus HPLC after heat resistance>0.1%, that is, if the difference between HPLC before and after heat resistance is greater than 0.1%, it can be judged as decomposition.

[0183] It can be seen from the data in Table 3 above that compared with the comparative compounds CP-1, CP-2, and CP-3, the compounds of the present invention have higher refractive indices under blue light, green light, and red light, which is beneficial to improving the light extraction efficiency of OLED devices. While the compounds of the present invention have higher refractive indices under blue light, green light, and red light, the refractive indices of the compounds of the present invention under blue light and red light have a suitable difference in the range of 0.22-0.26, which is beneficial to reduce color deviation and thus improve the visual deviation effect of the screen. The compounds of the present invention have a higher extinction coefficient at a wavelength of 380nm in the ultraviolet region, which will effectively absorb high-energy external light sources in the ultraviolet region to minimize damage to organic materials inside the organic light-emitting device, thereby helping to significantly improve the stability and service life of the organic light-emitting device.

[0184] As can be seen from the data in Table 4 above, compared with the comparative compound CP-3, the compound of the present invention has a lower evaporation temperature, and the decomposition temperature of the material is higher than the evaporation temperature of the material, thereby ensuring thermal stability at the evaporation temperature. In addition, the compound of the general formula (1) of the present invention has a higher refractive index in the visible light field, and after being applied as a covering layer to an OLED device, it can effectively improve the light extraction efficiency of the OLED device and reduce power consumption.

[0185] In summary, the compounds of the present invention have good thermal stability, a more suitable Eg energy level, a larger extinction coefficient k@380nm, and excellent refractive index under blue light, green light and red light, especially the refractive index under blue light and red light has a suitable difference range.

[0186] V Device Example

[0187] The following device examples are used to further illustrate the beneficial technical effects of the compounds of the present invention as a cover layer in OLED devices. 1. Materials, equipment and testing methods used in the examples

[0188] Source of materials: purchased from commercial sources or synthesized with reference to prior art literature.

[0189] The molecular structure formula of the relevant materials is shown below:

[0190]

[0191] equipment:

[0192] Vacuum evaporation device: Japan Choshu Industry 200*200mm evaporation equipment

[0193] Test method:

[0194] Determination of current efficiency, CIEx, CIEy, and just noticeable color difference (JNCD):

[0195] The IVL (current-voltage-luminance) test system (Suzhou Fushida Scientific Instrument Co., Ltd.) was used to test the OLED devices in the following device embodiments and device comparison examples, and the IVL characteristic curve, efficiency and current density relationship curve, color coordinate position and other data of the device were obtained. The test process must be carried out in a dark environment under the cover device. @10mA / cm 2 The data under the conditions shall prevail (i.e. the test current density reaches 10mA / cm 2 The corresponding performance values).

[0196] 2. Device Examples

[0197] (1) Covering layers with different film thicknesses

[0198] Devices comprising the compound of the present invention and comparative material CP-3 as covering layers were prepared, the thickness of the covering layers was changed, and the performance of the devices was measured.

[0199] The structure and manufacturing method of device embodiment 1-1:

[0200] Device structure: substrate layer 100 / first electrode (anode) layer 200 (ITO (15nm) / Ag (150nm) / ITO (15nm)) / hole injection layer 310 (HT-1:HI-1=97:3 mass ratio, thickness 10nm) / hole transport layer 320 (HT-1, thickness 135nm) / electron blocking layer 330 (EB-1, thickness 5nm) / light-emitting layer 340 (BH-1:BD-1=97:3 mass ratio, thickness 20nm) / hole blocking / electron transport layer 360 (ET-1:LiQ=1:1 mass ratio, thickness 35nm) / electron injection layer 370 (Yb, thickness 1nm) / second electrode (cathode) layer 400 (Mg:Ag=1:9 mass ratio, thickness 13nm) / covering layer 500 (compound 1 of the present invention, thickness 60nm).

[0201] Preparation method: The substrate layer is a PI film, and the ITO (15nm) / Ag (150nm) / ITO (15nm) anode layer is washed, that is, alkaline washing, pure water washing, drying, and then ultraviolet-ozone washing are performed in sequence to remove organic residues on the surface of the anode layer. On the anode layer after the above washing, a vacuum evaporation device is used to evaporate HT-1 and HI-1 with a film thickness of 10nm as a hole injection layer, and the mass ratio of HT-1 to HI-1 is 97:3. Then evaporate HT-1 with a thickness of 135nm as a hole transport layer. Then evaporate EB-1 with a thickness of 5nm as an electron blocking layer. After the above electron blocking material is evaporated, the light-emitting layer of the OLED light-emitting device is prepared, which uses BH-1 as the main material and BD-1 as the doping material. The mass ratio of BH-1 to BD-1 is 97:3, and the thickness of the light-emitting layer is 20nm. After the above-mentioned light-emitting layer, ET-1 and LiQ were vacuum-deposited. The mass ratio of ET-1 and LiQ was 1:1, and the film thickness was 35nm. This layer was a hole blocking / electron transport layer. On the hole blocking / electron transport layer, a Yb layer with a film thickness of 1nm was made by vacuum evaporation. This layer was an electron injection layer. On the electron injection layer, a Mg:Ag electrode layer with a film thickness of 13nm was made by vacuum evaporation. The mass ratio of Mg and Ag was 1:9. This layer was used as a cathode layer. On the cathode layer, the compound 1 of the present invention with a film thickness of 60nm was vacuum-deposited as a covering layer.

[0202] Device Examples 1-2 to 1-5

[0203] The device structure and manufacturing method are similar to those of device embodiment 1-1, except that the film thickness of the covering layer is 65 nm, 70 nm, 75 nm, and 80 nm, respectively, as shown in Table 5 below.

[0204] Comparative Device Examples 1-1 to 1-5

[0205] The device structure and manufacturing method are similar to those of device embodiment 1-1, except that: comparative compound CP-3 is used as the covering layer material of the OLED device; and the film thickness of the covering layer is 60nm, 65nm, 70nm, 75nm, and 80nm, respectively, as shown in Table 4 below.

[0206] Table 5

[0207]

[0208] Note: Index = current efficiency / CIEy, and it is only applicable to blue-light devices. The efficiency of blue-light devices is generally not based on current efficiency, but on Index (industry standard).

[0209] In the process of preparing devices by evaporation, the film thickness is erroneous and fluctuates. It is impossible to be accurate to within 1nm. It is very likely that the film thickness set by the equipment is 70nm, but the actual film thickness finally evaporated fluctuates within the range of 65-75nm, and may even fluctuate within a wider range, depending on the accuracy of the equipment itself. The wider the optimal film thickness range, the smaller the impact on the device efficiency. The fluctuation of Index within the range of 1% is considered to be the same level of device data. From the data in Table 5 above, it can be seen that compared with the comparative compound CP-3, when the cover layer is 60-80nm, the efficiency of the OLED device containing the compound 1 of the present invention (with index as reference data) fluctuates within the range of 220.09-227.06cd / A / CIEy; while the comparative compound CP-3, its fluctuation range is within the range of 199.78-209.55. Obviously, the efficiency of the OLED device containing the compound of the present invention is higher and the fluctuation amplitude is smaller, indicating that the device efficiency is less affected by the film thickness. Therefore, the manufacture of the device can allow a wider film thickness while also maintaining the stability of the high efficiency of the device.

[0210] (2) Preparation of blue light OLED devices

[0211] Blue light device embodiment B-1

[0212] Structure of blue light device embodiment B-1: substrate layer 100 / first electrode (anode) layer 200 (ITO (15nm) / Ag (150nm) / ITO (15nm)) / hole injection layer 310 (HT-1:HI-1=97:3 mass ratio, thickness 10nm) / hole transport layer 320 (HT-1, thickness 135nm) / electron blocking layer 330 (EB-1, thickness 5nm) / light-emitting layer 340 (BH-1:BD-1=97:3 mass ratio, thickness 20nm) / hole blocking / electron transport layer 360 (ET-1:LiQ=1:1 mass ratio, thickness 35nm) / electron injection layer 370 (Yb, thickness 1nm) / second electrode (cathode) layer 400 (Mg:Ag=1:9 mass ratio, thickness 13nm) / covering layer 500 (compound 1 of the present invention, thickness 70nm).

[0213] Preparation method: The substrate layer is a PI film, and the ITO (15nm) / Ag (150nm) / ITO (15nm) anode layer is washed, that is, alkaline washing, pure water washing, drying, and then ultraviolet-ozone washing are performed in sequence to remove organic residues on the surface of the anode layer. On the anode layer after the above washing, a vacuum evaporation device is used to evaporate HT-1 and HI-1 with a film thickness of 10nm as a hole injection layer, and the mass ratio of HT-1 to HI-1 is 97:3. Then, HT-1 with a thickness of 135nm is evaporated as a hole transport layer. Subsequently, EB-1 with a thickness of 5nm is evaporated as an electron blocking layer. After the above electron blocking material is evaporated, the light-emitting layer of the OLED light-emitting device is prepared, which uses BH-1 as the main material and BD-1 as the doping material. The mass ratio of BH-1 to BD-1 is 97:3, and the thickness of the light-emitting layer is 20nm. After the above-mentioned light-emitting layer, ET-1 and LiQ were vacuum-deposited, with a mass ratio of ET-1 to LiQ of 1:1 and a film thickness of 35nm. This layer was a hole blocking / electron transport layer. On the hole blocking / electron transport layer, a Yb layer with a film thickness of 1nm was made by vacuum evaporation, and this layer was an electron injection layer. On the electron injection layer, a Mg:Ag electrode layer with a film thickness of 13nm was made by vacuum evaporation, and the mass ratio of Mg to Ag was 1:9. This layer was used as a cathode layer. On the cathode layer, 70nm of the compound 1 of the present invention was vacuum-deposited as a covering layer.

[0214] Blue light device embodiments B-2 to B-15

[0215] The device structure and manufacturing method are similar to those of device embodiment B-1, except that other compounds of the present invention are used as covering layer materials; the specific compounds are shown in Table 6 below.

[0216] Comparative Examples of Blue Light Devices B-01 to B-02

[0217] The device structure and manufacturing method are similar to those of device embodiment B-1, except that a comparative compound is used as the covering layer material; the specific compounds are shown in Table 6 below.

[0218] The materials of the cover layer in the OLED device, the current efficiency of the device, CIEx, CIEy and the test data of the perceptible color difference are listed in Table 6.

[0219] Table 6

[0220]

[0221]

[0222] Note: Index = current efficiency / CIEy, and only applies to blue light devices. The efficiency of blue light devices is generally not based on current efficiency, but on Index (industry standard); Perceptible color difference, unit: JNCD; 1JNCD = 0.004

[0223] The data in Table 6 show that, compared with the blue light device comparative examples B-01 and B-02, the blue light OLED device prepared using the compound of the present invention as the cover layer has a significantly improved Index, and the perceptible color difference is smaller, so the angle change is smaller, and the color shift effect is significantly improved. It should be understood that the smaller the perceptible color difference and the smaller the chromaticity change, the better the angular dependence of the wavelength of the emitted light of the organic electroluminescent device is suppressed.

[0224] In summary, the compound of the present invention is used as a cover layer in an OLED device, which greatly improves the light extraction efficiency, significantly improves the current efficiency and improves the angle dependence.

[0225] In summary, the above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. An aromatic amine organic compound, characterized in that: The structure of the aromatic amine organic compound is shown in general formula (1): In the general formula (1), X represents O or S; m represents 1 or 2; R1 and R2 each independently represent a hydrogen atom or a phenyl group; When R1 and R2 are independently represented by phenyl, the phenyl is connected to the main structure in a ring through a CM1-CM2 bond, a CM2-CM3 bond, a CM3-CM4 bond, a CM5-CM6 bond, a CM6-CM7 bond or a CM7-CM8 bond; L and L1 are independently a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, or a substituted or unsubstituted naphthylene group; Ar1 represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted naphthobenzofuranyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted N-phenylcarbazolyl group, a substituted or unsubstituted dibenzothienyl group, a substituted or unsubstituted benzoxazolyl group, a substituted or unsubstituted benzothiazolyl group, a substituted or unsubstituted naphthofuranyl group, a substituted or unsubstituted naphthothienyl group, or a substituted or unsubstituted benzo[4,5]imidazo[1,2-a]pyridyl group; The substituent for the substituent group is selected from one or more of a deuterium atom, a cyano group, a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a benzoxazolyl group, a benzothiazolyl group, a benzimidazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a naphthofuranyl group, and a naphthothiophenyl group.

2. The aromatic amine organic compound according to claim 1, characterized in that: The structure of the aromatic amine organic compound is shown in any one of the general formulas (3) to (9); The definitions of X, L, L1, and Ar1 are the same as those in claim 1.

3. The aromatic amine organic compound according to claim 1, characterized in that: The structure of the aromatic amine organic compound is shown in any one of the general formulas (10) to (15); The definitions of X, L, L1, and Ar1 are the same as those in claim 1.

4. The aromatic amine organic compound according to claim 1, characterized in that: The structure of the aromatic amine organic compound is shown in general formula (16) or general formula (17); The X1 is represented by -O- or -S-; the definitions of X, L, L1 are the same as those in claim 1.

5. The aromatic amine organic compound according to claim 1, characterized in that: The L and L1 independently represent one or more of a single bond, a phenylene group, a biphenylene group, and a naphthylene group; The Ar1 represents one of phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, triphenylene, carbazolyl, naphthiobenzofuranyl, dibenzofuranyl, N-phenylcarbazolyl, dibenzothiophenyl, benzoxazolyl, benzothiazolyl, naphthiofuranyl, naphthiophenyl, and benzo[4,5]imidazo[1,2-a]pyridyl.

6. The aromatic amine organic compound according to claim 1, characterized in that: The specific structure of the aromatic amine organic compound is any one of the following structures:

7. The aromatic amine organic compound according to any one of claims 1 to 6, characterized in that: The extinction coefficient of the aromatic amine organic compound at a wavelength of 380nm is 0.8-1.3; the refractive index under blue light with a wavelength of 450nm is 2.33-2.40; the refractive index under green light with a wavelength of 525nm is 2.17-2.23; the refractive index under red light with a wavelength of 620nm is 2.10-2.16; and the difference in refractive index under blue light and red light is 0.20-0.27; the evaporation temperature of the aromatic amine organic compound is lower than the decomposition temperature, and the evaporation temperature is 300-360°C.

8. The aromatic amine organic compound according to claim 7, characterized in that: The refractive index of the aromatic amine organic compound under blue light with a wavelength of 450nm is 2.35-2.40; the refractive index under red light with a wavelength of 620nm is 2.11-2.16; and the difference in refractive index under blue light and red light is 0.20-0.26; the evaporation temperature of the aromatic amine organic compound is 300-350°C.

9. The aromatic amine organic compound according to claim 8, characterized in that: The difference in refractive index between the aromatic amine organic compound under blue light and red light is 0.22-0.26; and the evaporation temperature of the aromatic amine organic compound is 330-350°C.

10. An organic electroluminescent device, comprising: substrate layer; a first electrode, the first electrode being on the substrate; An organic light-emitting functional layer, the organic light-emitting functional layer is on the first electrode; A second electrode, the second electrode being on the organic light-emitting functional layer; and a covering layer on the second electrode; Characterized in that the covering layer comprises the aromatic amine organic compound according to any one of claims 1-6.

11. The organic electroluminescent device according to claim 10, characterized in that: The thickness of the covering layer is 10-1000 nm.

12. The organic electroluminescent device according to claim 11, characterized in that: The thickness of the cover layer is preferably 40-140 nm.

13. The organic electroluminescent device according to claim 12, characterized in that: The thickness of the cover layer is more preferably 50-90 nm.

14. The organic electroluminescent device according to claim 13, characterized in that: The thickness of the covering layer is more preferably 60 nm to 80 nm.

15. The organic electroluminescent device according to claim 14, characterized in that: The thickness of the cover layer is most preferably 65-75 nm.

16. The organic electroluminescent device according to claim 10, characterized in that: The organic electroluminescent device comprises one or more combinations of blue, green or red organic light-emitting material layers; different organic light-emitting material layers are stacked and combined horizontally or vertically.

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