A compound containing triazine and phenanthrene structure and its application in organic electroluminescent device

Abstract

The application discloses a compound containing triazine and phenanthrene structures and application thereof to an organic electroluminescent device, and belongs to the technical field of semiconductor materials. The compound has good stability and electron resistance, and has good electron injection and electron transmission capacity. When the compound is used as a material of the organic electroluminescent device, the driving voltage, the device efficiency and the device life of the device are significantly improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of semiconductor materials, in particular to a compound containing triazine and phenanthrene structure and application thereof in organic electroluminescent devices. BACKGROUND

[0002] Organic electroluminescent device (OLED: Organic Light Emission Diodes) technology can be used to manufacture new display products and new lighting products, and is expected to replace existing liquid crystal display and fluorescent lamp lighting, and has a very wide application prospect. OLED device has a sandwich-like structure, including electrode material film layers and organic functional materials sandwiched between different electrode material film layers, various different organic functional materials are stacked together according to the purpose to jointly constitute the OLED light-emitting device. OLED light-emitting device as a current device, when a voltage is applied to the two electrodes thereof, and the electric field acts on the positive and negative charges in the organic layer functional material film layer, the positive and negative charges are further recombined in the light-emitting layer, that is, OLED electroluminescence is generated.

[0003] At present, OLED display technology has been applied in the field of smart phones, tablet computers and other fields, and will further expand to large-size application fields such as televisions. However, compared with the actual product application requirements, the performance of OLED devices such as luminous efficiency and service life needs to be further improved. In order to continuously improve the performance of OLED devices, OLED optoelectronic functional materials need to be continuously researched and innovated, and higher performance OLED functional materials need to be created.

[0004] OLED optoelectronic functional materials applied to OLED devices can be divided into two categories in terms of use, which are charge injection and transport materials and light-emitting materials. Further, the 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. As charge transport materials, they require good carrier mobility, high glass transition temperature, etc. For OLED devices, electrons are injected from the cathode, then transmitted through the electron transport layer to the host material, and then recombined with holes in the host material to generate excitons. Therefore, improving the injection and transmission capacity of the electron transport layer is beneficial to reducing the device driving voltage and obtaining high efficiency of electron-hole recombination. Therefore, the electron transport layer is very important and needs to have high efficiency of electron injection, transmission and high durability.

[0005] With the significant progress of OLED devices, the performance requirements of materials are also increasing, not only requiring good material stability, but also requiring good efficiency and service life at low driving voltage. However, the current electron transport material has insufficient electron injection and transport capacity and heat resistance stability, and the material has defects in electron resistance, which causes the material to separate or decompose during device operation, thereby causing poor device service life. SUMMARY

[0006] In view of the above problems existing in the prior art, the present application provides a compound containing triazine and phenanthrene and its application in an organic electroluminescent device. The compound of the present application is bridged by a specific structure of triphenyl or pyrimidine substituted biphenyl, and the bridging structure is a triangular framework, so that the compound has excellent electron injection and transport capacity, and is applied to an organic electroluminescent device, which can effectively reduce the working voltage of the device and improve the luminous efficiency and service life of the device.

[0007] The technical scheme of the present application is as follows:

[0008] A compound containing triazine and phenanthrene structure, the structure of the compound is shown in any one of general formula (1-1) to general formula (1-3):

[0009]

[0010]

[0011] In general formula (1-1) to general formula (1-3), R1 represents phenyl, naphthyl or biphenyl;

[0012] Z1, Z2, Z3 independently represent C-H or N atom.

[0013] Further preferably, the structure of the compound is shown in any one of general formula (2-1) to general formula (2-12):

[0014]

[0015] In general formula (2-1) to general formula (2-12), the meaning of R1 is the same as defined above; the connection sites of phenanthrene and other groups are L1, L2, L3, L4 or L5.

[0016] Further preferably, the structure of the compound is shown in any one of general formula (3-1) to general formula (3-12):

[0017]

[0018] In general formula (3-1) to general formula (3-12), the meaning of R1 is the same as defined above.

[0019] Further preferably, R1in the compound containing triazine and phenanthrene structure represents phenyl.

[0020] Further preferably, R1in the compound containing triazine and phenanthrene structure represents biphenyl.

[0021] Further preferably, R1in the compound containing triazine and phenanthrene structure represents naphthyl.

[0022] Preferably, the specific structure of the compound is any one of the following structures:

[0023]

[0024]

[0025]

[0026]

[0027]

[0028]

[0029]

[0030]

[0031]

[0032]

[0033]

[0034]

[0035]

[0036]

[0037] An organic electroluminescent device comprising a first electrode and a second electrode, between which there is a plurality of organic thin film layers, at least one of the organic thin film layers containing the compound containing triazine and phenanthrene structure.

[0038] Preferably, the organic thin film layer includes an electron transport layer, the electron transport layer containing the compound containing triazine and phenanthrene structure.

[0039] An organic electroluminescent device comprising, in this order, a first electrode, a hole transport region, a light emitting region, an electron transport region, and a second electrode, wherein the electron transport region contains the compound containing triazine and phenanthrene structure.

[0040] Preferably, the electron transport region comprises an electron transport layer and a hole blocking layer.

[0041] Preferably, the electron transport region comprises an electron transport layer, and the electron transport layer contains the compound containing triazine and phenanthrene structure.

[0042] Preferably, the electron transport layer contains Liq and the compound containing triazine and phenanthrene structure.

[0043] A display element containing the organic electroluminescent device.

[0044] The present application has the beneficial technical effects in that:

[0045] The compound of the present application is based on triazine and phenanthrene structure, and the triazine and phenanthrene groups are connected by a specific triphenyl or pyrimidine substituted biphenyl bridging group to form a triangular architecture bridging feature. Such compound has good electron tolerance and stability, and has good electron injection and transport capacity. Therefore, when used as an electron transport material of the functional layer of OLED, it can effectively reduce the driving voltage of the device, and improve the photoelectric performance and device life of the OLED device.

[0046] The triazine structure compound of the present application can further delocalize the LUMO electron cloud distribution of the material, improve the electron tolerance of the material, and effectively improve the electron stability of the material. In addition, the phenanthrene group is introduced in the present application, which has a vertical structure and can inhibit the π-π stacking between molecules, significantly improve the electron mobility of the molecule, and reduce the driving voltage of the device. And due to the presence of the phenanthrene group in the present application, the glass transition temperature of the material is improved, and the stability of the thin film of the material is effectively improved. Therefore, the driving voltage of the device can be effectively reduced, and the service life of the device can be improved. BRIEF DESCRIPTION OF DRAWINGS

[0047] Figure 1 The structure diagram of the OLED device using the material listed in the present application.

[0048] In the figure, 1 is a transparent substrate layer, 2 is an anode layer, 3 is a hole injection layer, 4 is a hole transport layer, 5 is an electron blocking layer, 6 is a light emitting layer, 7 is a hole blocking layer, 8 is an electron transport layer, 9 is an electron injection layer, 10 is a cathode layer, and 11 is a CPL layer. DETAILED DESCRIPTION

[0049] The technical solutions of the present application will be described in detail below in combination with the drawings and embodiments.

[0050] In the drawings, the size of layers and regions can be exaggerated for clarity. It will also be understood that when a layer or element is referred to as being "on" another layer or substrate, it can be directly on the other layer or substrate, or intervening layers can also be present. In addition, it will also be understood that when a layer is referred to as being "between" two layers, it can be the only layer between the two layers, or one or more intervening layers can also be present. Like reference numerals refer to like elements throughout.

[0051] In this application, the terms "upper", "lower", and the like, when used in describing the orientation of the electrode and the organic electroluminescent device, and other structures, are used for convenience only and do not imply any particular orientation of the relevant structure; rather, the relevant structure can be oriented in any direction, and the designation of "upper" and "lower" is merely intended to simplify the description of the application. Specifically, in this application, the "lower" side of the electrode refers to the side of the electrode that is closer to the substrate during the manufacturing process, and the opposite side, which is farther from the substrate, is the "upper" side.

[0052] Organic electroluminescent device

[0053] In another embodiment of the present application, there is provided an organic electroluminescent device comprising a first electrode (anode), a second electrode (cathode), and a plurality of organic thin film layers between the first electrode and the second electrode, wherein at least one of the organic thin film layers contains the compound containing triazine and phenanthrene structure according to the present application.

[0054] In a preferred embodiment of the present application, the organic thin film layers comprise an electron transport layer, wherein the electron transport layer contains the compound containing triazine and phenanthrene structure according to the present application.

[0055] Preferably, the electron transport layer contains, in addition to the organic compound according to the present application, another electron transport material, such as Liq (see the examples for the specific chemical structure).

[0056] In a preferred embodiment of the present application, the organic electroluminescent device according to the present application comprises a substrate, a first electrode layer (anode layer), organic thin film layers, and a second electrode layer (cathode layer), wherein the organic thin film layers comprise, but are 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 blocking layer, and / or an electron injection layer.

[0057] The preferred device structure of the present application is in the form of top emission. Preferably, the anode of the organic electroluminescent device according to the present application employs an electrode with high reflectivity, preferably ITO / Ag / ITO; and the cathode employs a transparent electrode, preferably a mixed electrode of Mg:Ag = 1:9, so as to form a microcavity resonance effect, and the device emits light from the side of the Mg:Ag electrode.

[0058] In a preferred embodiment of the present application, there is provided an organic electroluminescent device comprising a substrate, an anode, a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a cathode layer, wherein the anode is on the substrate, the hole injection layer is on the anode, the hole transport layer is on the hole injection layer, the electron blocking layer is on the hole transport layer, the light-emitting layer is on the hole transport layer, the electron transport layer is on the light-emitting layer, the electron injection layer is on the electron transport layer, and the cathode layer is on the electron injection layer.

[0059] As the substrate of the organic electroluminescent device of the present application, any substrate conventionally used for organic electroluminescent devices can be used. Examples are transparent substrates such as glass or transparent plastic substrates; non-transparent substrates such as silicon substrates; flexible PI film substrates. Different substrates have different mechanical strength, thermal stability, transparency, surface smoothness, water resistance. Depending on the properties of the substrate, the direction of use is different. In the present application, the use of a transparent substrate is preferred. The thickness of the substrate is not particularly limited.

[0060] On the substrate, a first electrode (anode) is formed, and the anode material is preferably a material having a high work function so that holes are easily injected into the organic functional material layer. Non-limiting examples of the anode material include, but are not limited to, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (Sn02), 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 multi-layer structure comprising 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, and is typically 50-500 nm, preferably 70-300 nm and more preferably 100-200 nm.

[0061] A hole injection layer 3, a hole transport layer 4, and an electron blocking layer 5 can be provided between the anode 2 and the light-emitting layer 6.

[0062] 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 group consisting of a quinone derivative, such as tetracyanoquinodimethane (TCNQ) or 2,3,5,6-tetrafluoro-tetracyano-1,4-benzoquinone dimethane (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:

[0063]

[0064] According to the present application, P1 is preferably used as the P dopant. The ratio of the hole transport layer to the P dopant used in the present application is 99:1 to 70:30, preferably 99:1 to 85:15 and more preferably 97:3 to 87:13, based on mass.

[0065] The thickness of the hole injection layer of the present application can be 1 to 100 nm, preferably 2 to 50 nm and more preferably 5 to 20 nm.

[0066] The material of the hole transport layer is preferably a material having a high hole mobility, which enables the transfer of holes 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 pyridinoline derivative, a polysilane derivative, an imidazole derivative, a phenylenediamine derivative, an amino-substituted chalcone derivative, a styrylanthracene derivative, a styrylamine derivative and the like styryl compound, a fluorene derivative, a spirofluorene derivative, a silazane derivative, an aniline-based copolymer, a porphyrin compound, a carbazole derivative, a polyarylalkane derivative, a polyphenylenevinylene and a derivative thereof, a polythiophene and a derivative thereof, a poly-N-vinylcarbazole derivative, a conductive polymer oligomer such as a thiophene oligomer, an aromatic tertiary amine compound, a styrylamine compound, a triamine, a tetraamine, a benzidine, a propargyl diamine derivative, a p-phenylenediamine derivative, a m-phenylenediamine derivative, 1,1'-bis(4-diarylamino phenyl)cyclohexane, 4,4'-bis(diarylamines) biphenyls, bis[4-(diarylamino)phenyl]methane, 4,4"-bis(diarylamino)terphenyls, 4,4"'-bis(diarylamino)quaterphenyls, 4,4'-bis(diarylamino)diphenyl ethers, 4,4'-bis(diarylamino)diphenyl sulfides, bis[4-(diarylamino)phenyl]dimethylmethane, bis[4-(diarylamino)phenyl]-bis(trifluoromethyl)methane or a 2,2-diphenylethene compound and the like.

[0067] The thickness of the hole transport layer of the present application can be 5 to 200 nm, preferably 10 to 180 nm and more preferably 20 to 150 nm.

[0068] The electron blocking layer requires that the triplet (T1) energy level of the material is higher than the T1 energy level of the host material in the light emitting layer, which can block 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 light emitting layer host material, which is conducive to the injection of holes from the positive electrode into the light emitting layer, and at the same time requires that the electron blocking layer material has high hole mobility, which is conducive to hole transport and reduces the power consumption of the device; the LUMO energy level of the electron blocking layer material is higher than the LUMO energy level of the light emitting layer host material, which plays a role in blocking electrons, that is, the electron blocking layer material requires a wide band gap (Eg). The electron blocking layer material meeting the above conditions can be a triarylamine derivative, a fluorene derivative, a spirofluorene derivative, a dibenzofuran derivative, a carbazole derivative, etc. Among them, the triarylamine derivative is 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; the spirofluorene derivative is, such as N-([1,1'-diphenyl]-4-yl)-N-(9,9-dimethyl-9H-furan-2-yl)-9,9'-spirobifluorene-2-amine; the dibenzofuran derivative is, such as N,N-di([1,1'-biphenyl]-4-yl)-3'-(dibenzo[b,d]furan-4-yl)-[1,1'-biphenyl]-4-amine, but is not limited thereto.

[0069] According to the present application, the thickness of the electron blocking layer can be 1-200 nm, preferably 5-150 nm, and more preferably 10-100 nm.

[0070] According to the present application, the light emitting layer is located between the first electrode and the second electrode. The material of the light emitting layer is a material capable of emitting 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 can include a host material and a dopant material. As the host material and the guest material of the light emitting layer of the organic electroluminescent device of the present application, the host material can be one or a combination of two of anthracene derivatives, quinoxaline derivatives, triazine derivatives, xanthone derivatives, benzophenone derivatives, carbazole derivatives, pyridine derivatives, or pyrimidine derivatives. The guest material can be a pyrene derivative, a boron derivative, a fluorene derivative, a spirofluorene derivative, an iridium complex, or a platinum complex.

[0071] A hole blocking layer can be disposed on the light emitting layer. The hole blocking layer material has a triplet (T1) energy level higher than the T1 energy level of the host material of the light emitting layer, which can block 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 host material of the light emitting layer, which plays a role in blocking holes, and at the same time requires the hole blocking layer material to have high electron mobility, which is beneficial for electron transport and reduces the power consumption of the device; the hole blocking layer material meeting the above conditions can be a triazine derivative, an azabenzenes derivative, etc. Among them, the triazine derivative is preferred; but not limited thereto.

[0072] The thickness of the hole blocking layer of the present application can be 2-200 nm, preferably 5-150 nm, and more preferably 10-100 nm, but the thickness is not limited to this range.

[0073] An electron transport layer can 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. The electron transport layer includes one or more compounds containing triazine and phenanthrene structures of the present application. Preferably, the electron transport layer is composed of the organic compound of the present application and other electron transport layer materials. More preferably, the other electron transport layer material is a material commonly used in the art. Most preferably, the electron transport layer is composed of the compound containing triazine and phenanthrene structures of the present application and Liq.

[0074] The thickness of the electron transport layer of the present application can be 10-80 nm, preferably 20-60 nm, and more preferably 25-45 nm.

[0075] In the electron transport layer of the organic electroluminescent device according to the present application, the ratio of the compound containing triazine and phenanthrene structures of the present application to the other electron transport layer material is 1:9-9:1, preferably 2:8-8:2, more preferably 4:6-6:4, and most preferably 5:5.

[0076] As the electron transport compound of the present application, one or more of the compounds containing triazine and phenanthrene structures are preferably used.

[0077] The electron injection layer material is preferably a metal Yb having 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 application can be 0.1-5 nm, preferably 0.5-3 nm, and more preferably 0.8-1.5 nm.

[0078] The second electrode can be a cathode, and the material used to form the cathode can be a material with low work function, such as metals, alloys, conductive compounds, or mixtures thereof. Non-limiting examples of cathode materials can include lithium (Li), ytterbium (Yb), magnesium (Mg), aluminum (Al), calcium (Ca), as well as aluminum-lithium (Al-Li), magnesium-indium (Mg-In), and magnesium-silver (Mg-Ag). The thickness of the cathode depends on the material used, typically 5-100 nm, preferably 7-50 nm, and more preferably 10-25 nm.

[0079] Optionally, to improve the light extraction efficiency of the organic electroluminescent device, a light extraction layer (i.e., a CPL layer) can be added above the second electrode (i.e., the cathode) of the device. According to the principles of optical absorption and refraction, the CPL layer material should have a higher refractive index and a lower absorption coefficient. Any material known in the art can be used as the CPL layer material, such as Alq3. The thickness of the CPL layer is typically 5-300 nm, preferably 20-100 nm, and more preferably 40-80 nm.

[0080] Optionally, the organic electroluminescent device may also include an encapsulation structure. The encapsulation structure may be a protective structure preventing external substances such as moisture and oxygen from entering the organic layer of the organic electroluminescent device. The encapsulation structure may be, for example, a can, such as a glass or metal can; or a thin film covering the entire surface of the organic layer.

[0081] Methods for fabricating organic electroluminescent devices

[0082] The present invention also relates to a method for fabricating the above-mentioned organic electroluminescent device, comprising sequentially laminating a first electrode, a multilayer organic thin film layer, and a second electrode on a substrate. The multilayer organic thin film layer is formed by sequentially laminating a hole transport region, a light-emitting layer, and an electron transport region on the first electrode from bottom to top. The hole transport region is formed by sequentially laminating a hole injection layer, a hole transport layer, and an electron blocking layer on the first electrode from bottom to top, and the electron transport region is formed by sequentially laminating a hole blocking layer, an electron transport layer, and an electron injection layer on the light-emitting layer from bottom to top. Optionally, a CPL layer may also be laminated on the second electrode to improve the light extraction efficiency of the organic electroluminescent device.

[0083] Regarding lamination, methods such as vacuum deposition, vacuum evaporation, spin coating, casting, LB method, inkjet printing, laser printing, or LITI can be used, but are not limited to these. Among them, vacuum evaporation refers to heating the material and depositing it onto the substrate in a vacuum environment.

[0084] In this invention, vacuum evaporation is preferably used to form the various layers, wherein the vapor deposition process can be carried out at a temperature of about 100-500°C for about 10... -8 -10 -2 The vacuum degree and about The vacuum evaporation is preferably performed at a rate of 0.1 A / sec to 1 A / sec. The vacuum degree is preferably 10 -6 -10 -2 Torr, more preferably 10 -5 -10 -3 Torr. The rate is about 0.1 A / sec to 1 A / sec. More preferably, the rate is about 0.1 A / sec to 0.5 A / sec.

[0085] Further, it is to be noted that the materials used to form the respective layers according to the present application can be used as a single layer by being deposited as a single layer, can be used as a single layer by being deposited after being mixed with other materials, and can be used as a single layer by being deposited as a stacked structure of layers deposited as single layers and layers deposited after being mixed with other materials.

[0086] Display element

[0087] The present application also relates to a display device including the organic electroluminescent device described above, particularly a flat panel display device. In a preferred embodiment, the display device can include one or more organic electroluminescent devices described above, and in the case of including a plurality of devices, the devices are combined in a lateral or longitudinal stack. The display device can further include at least one thin film transistor. The thin film transistor can 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 can be electrically connected to the first electrode of the organic electroluminescent device. The active layer can include crystalline silicon, amorphous silicon, an organic semiconductor, or an oxide semiconductor, but is not limited thereto.

[0088] Examples

[0089] I. Preparation of compounds

[0090] The starting materials involved in the synthesis examples according to the present application can be commercially available or prepared by conventional methods in the art;

[0091] The starting materials A1, A2, A3, A4, A5, A6, A7, E1, E2, E3, and E4 can be commercially available or prepared by conventional methods in the art;

[0092]

[0093] Preparation of intermediate C1:

[0094]

[0095] In a 500ml round-bottom flask, under nitrogen protection, raw material A1 (30mmol), raw material B1 (33mmol), KOAC (90mmol), dioxane (200mL) were added in turn, and the air was replaced with nitrogen for 30min. Pd(PPh3)4 (0.6mmol) was added, and the reaction was heated to reflux under nitrogen protection for 12h. The reaction liquid was detected by TCL, and it was found that raw material A1 was completely reacted. After the reaction was completed, the reaction system was naturally cooled to room temperature, poured into a separatory funnel, shaken, and then allowed to stand to separate layers. The aqueous phase was extracted with dichloromethane (50ml*3), and the organic phase was combined and dried with anhydrous magnesium sulfate. After filtration, the filtrate was concentrated by rotary evaporation to remove dichloromethane to obtain intermediate C1. LC-MS: measured value: 436.32 ([M+H] + ); accurate mass: 435.21.

[0096] Intermediate C was prepared by a similar method to the synthesis of intermediate C1, and the raw materials A and B used are shown in Table 1

[0097] Table 1

[0098]

[0099]

[0100] Preparation of intermediate D1, intermediate E1, and intermediate F1:

[0101]

[0102]

[0103] In a 500ml round-bottom flask, under nitrogen protection, raw material C1 (30mmol), raw material D1 (30mmol), K2CO3 (90mmol), tetrahydrofuran (180mL), water (60mL) were added in turn, and the air was replaced with nitrogen for 30min. Pd(PPh3)4 (0.6mmol) was added, and the reaction was heated to reflux under nitrogen protection for 12h. The reaction liquid was detected by TCL, and it was found that raw material C1 was completely reacted. 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 dissolved in dichloromethane 150ml, washed with water 100ml, poured into a separatory funnel, shaken, and then allowed to stand to separate layers. The aqueous phase was extracted with dichloromethane (50ml*3), and the organic phase was combined and dried with anhydrous magnesium sulfate. After filtration, the filtrate was concentrated by rotary evaporation to remove dichloromethane to obtain the crude product, which was purified by silica gel column chromatography to obtain intermediate D1. LC-MS: measured value: 266.91 ([M+H] + ); accurate mass: 265.95.

[0104] In a 500ml round bottom flask, under nitrogen protection, raw material E1 (30mmol), diethyl ether (150mL) were added in turn, cooled to -78°C, replaced with nitrogen for 30min, 1.6mol / L n-butyllithium hexane solution (40mmol) was slowly added, and kept at -78°C for 3h, then trimethyl borate (40mmol) was added, kept at -78°C for 1h, then the mixture was allowed to react at room temperature for 16h. TLC detection of the reaction liquid showed that raw material E1 was completely reacted. After the reaction was completed, a dilute hydrochloric acid solution (50ml) was added to the reaction system, the organic solvent was removed by rotary evaporation, and the residue was filtered to obtain white solid intermediate E1. LC-MS: measured value: 278.21 ([M+H] + ); accurate mass: 277.10.

[0105] In a 500ml round bottom flask, under nitrogen protection, intermediate D1 (15mmol), intermediate E1 (15mmol), K2CO3 (45mmol), tetrahydrofuran (180mL), water (60mL) were added in turn, replaced with nitrogen for 30min, Pd(PPh3)4 (0.3mmol) was added, and heated to reflux under nitrogen protection for 12h. TLC detection of the reaction liquid showed that intermediate D1 was completely reacted. After the reaction was completed, the reaction system was naturally cooled to room temperature, the solvent was removed by rotary evaporation, the residue was dissolved in dichloromethane 150ml, washed with water 100ml, poured into a separatory funnel, shaken and then allowed to stand to separate the layers, the aqueous phase was extracted with dichloromethane (50ml*3), the organic phase was combined and dried with anhydrous magnesium sulfate, filtered, and the filtrate was rotary evaporated to remove dichloromethane to obtain a crude product, which was purified by silica gel column chromatography to obtain intermediate F1. LC-MS: measured value: 420.20 ([M+H] + ); accurate mass: 419.12.

[0106] Intermediate D was prepared by a similar synthesis method as intermediate D1, and the raw material C and raw material D used are shown in Table 2;

[0107] Intermediate E was prepared by a similar synthesis method as intermediate E1, and the raw material E used is shown in Table 2;

[0108] Intermediate F was prepared by a similar synthesis method as intermediate F1, and the intermediate D and intermediate E used are shown in Table 2;

[0109] Table 2

[0110]

[0111]

[0112]

[0113] Example 1: Synthesis of compound 2

[0114]

[0115] In a 250 ml round bottom flask, under nitrogen protection, intermediate F5 (20 mmol), intermediate C7 (22 mmol), K2CO3 (60 mmol), tetrahydrofuran (100 mL), water (50 mL) were added in turn, nitrogen was replaced for 30 min to replace air, palladium acetate (0.20 mmol) was added, 2-dicyclohexylphosphine-2',4',6'-triisopropyl biphenyl (0.40 mmol), heated to reflux under nitrogen protection for 11 h. The reaction liquid was detected by TCL and it was found that intermediate F5 was completely reacted. After the reaction was completed, the reaction system was naturally cooled to room temperature, the solvent was removed by rotary evaporation, the residue was dissolved in dichloromethane 200 ml, washed with water 150 ml, poured into a separatory funnel, shaken and then separated, the aqueous phase was extracted with dichloromethane (80 ml*3), the organic phase was combined and dried with anhydrous magnesium sulfate, filtered, and the filtrate was rotary evaporated to remove dichloromethane to obtain a crude product, which was purified by silica gel column chromatography to obtain compound 2. Elemental analysis: C 47 H 31 N3; Theoretical value: C, 88.51; H, 4.90; N, 6.59; Test value: C, 88.44; H, 5.10; N, 6.57. LC-MS: measured value: 638.55 ([M+H] + ), accurate mass: 637.25.

[0116] Example 2: Synthesis of compound 17

[0117]

[0118] Compound 17 was prepared according to the synthesis method of compound 2 in Example 1, except that intermediate F6 was used instead of intermediate F5. Elemental analysis: C 53 H 35 N3 theoretical value: C, 89.17; H, 4.94; N, 5.89; test value: C, 89.15; H, 4.96; N, 5.81. LC-MS: measured value: 714.19 ([M+H] + ), accurate mass: 713.28.

[0119] Example 3: Synthesis of compound 62

[0120]

[0121] Compound 62 was prepared according to the synthesis method of compound 2 in Example 1, except that intermediate F8 was used instead of intermediate F5. Elemental analysis: C 51 H33 N3; Calc. C, 89.05; H, 4.84; N, 6.11; Found C, 89.08; H, 5.01; N, 6.04. LC-MS: Obs. 688.55 ([M+H] + ), exact mass: 687.27.

[0122] Example 4: Synthesis of compound 77

[0123]

[0124] Compound 77 was prepared according to the procedure described for the synthesis of compound 2 in Example 1, except that intermediate F7 was used instead of intermediate F5. Elemental Analysis: C 51 H 33 N3; Calc. C, 89.05; H, 4.84; N, 6.11; Found C, 89.08; H, 5.01; N, 6.04. LC-MS: Obs. 688.55 ([M+H] + ), exact mass: 687.27.

[0125] Example 5: Synthesis of compound 92

[0126]

[0127] Compound 92 was prepared according to the procedure described for the synthesis of compound 2 in Example 1, except that intermediate F9 was used instead of intermediate F5, and intermediate C1 was used instead of intermediate C7. Elemental Analysis: C 47 H 31 N3; Calc. C, 88.51; H, 4.90; N, 6.59; Found C, 88.72; H, 4.63; N, 6.55. LC-MS: Obs. 638.17 ([M+H] + ), exact mass: 637.25.

[0128] Example 6: Synthesis of compound 95

[0129]

[0130] Compound 95 was prepared according to the procedure described for the synthesis of compound 2 in Example 1, except that intermediate F9 was used instead of intermediate F5, and intermediate C3 was used instead of intermediate C7. Elemental Analysis: C 53 H 35 N3; Calc. C, 89.17; H, 4.94; N, 5.89; Found C, 89.23; H, 4.80; N, 5.76. LC-MS: Obs. 714.39 ([M+H] + ), exact mass: 713.28.

[0131] Example 7: Synthesis of compound 98

[0132]

[0133] Compound 98 was prepared according to the procedure described in Example 1 for the synthesis of compound 2, except that intermediate F9 was used in place of intermediate F5 and intermediate C2 was used in place of intermediate C7. Elemental Analysis: C 53 H 35 N3; Theoretical: C, 89.17; H, 4.94; N, 5.89; Found: C, 89.03; H, 5.05; N, 6.14. LC-MS: Found: 714.23 ([M+H] + ), Exact Mass: 713.28.

[0134] Example 8: Synthesis of compound 101

[0135]

[0136] Compound 101 was prepared according to the procedure described in Example 1 for the synthesis of compound 2, except that intermediate F9 was used in place of intermediate F5 and intermediate C4 was used in place of intermediate C7. Elemental Analysis: C 53 H 35 N3; Theoretical: C, 89.17; H, 4.94; N, 5.89; Found: C, 89.12; H, 4.84; N, 5.94. LC-MS: Found: 714.52 ([M+H] + ), Exact Mass: 713.28.

[0137] Example 9: Synthesis of compound 104

[0138]

[0139] Compound 104 was prepared according to the procedure described in Example 1 for the synthesis of compound 2, except that intermediate F9 was used in place of intermediate F5 and intermediate C6 was used in place of intermediate C7. Elemental Analysis: C 51 H 33 N3; Theoretical: C, 89.05; H, 4.84; N, 6.11; Found: C, 89.17; H, 4.97; N, 5.99. LC-MS: Found: 688.60 ([M+H] + ), Exact Mass: 687.27.

[0140] Example 10: Synthesis of compound 107

[0141]

[0142] Compound 107 was prepared according to the procedure for the synthesis of Compound 2 in Example 1, except that intermediate F9 was used in place of intermediate F5, and intermediate C5 was used in place of intermediate C7. Elemental Analysis: C 51 H 33 N3; Calc: C, 89.05; H, 4.84; N, 6.11; Found: C, 88.95; H, 4.96; N, 6.09. LC-MS: Obs. 688.41 ([M+H] + ), Exact Mass: 687.27.

[0143] Example 11: Synthesis of Compound 110

[0144]

[0145] Compound 110 was prepared according to the procedure for the synthesis of Compound 2 in Example 1, except that intermediate F10 was used in place of intermediate F5, and intermediate C1 was used in place of intermediate C7. Elemental Analysis: C 47 H 31 N3; Calc: C, 88.51; H, 4.90; N, 6.59; Found: C, 88.41; H, 5.01; N, 6.34. LC-MS: Obs. 638.54 ([M+H] + ), Exact Mass: 637.25.

[0146] Example 12: Synthesis of Compound 128

[0147]

[0148] Compound 128 was prepared according to the procedure for the synthesis of Compound 2 in Example 1, except that intermediate F11 was used in place of intermediate F5, and intermediate C1 was used in place of intermediate C7. Elemental Analysis: C 47 H 31 N3; Calc: C, 88.51; H, 4.90; N, 6.59; Found: C, 88.42; H, 4.86; N, 6.40. LC-MS: Obs. 638.49 ([M+H] + ), Exact Mass: 637.25.

[0149] Example 13: Synthesis of Compound 146

[0150]

[0151] Compound 146 was prepared according to the procedure for the synthesis of Compound 2 in Example 1, except that intermediate F12 was used in place of intermediate F5, and intermediate C1 was used in place of intermediate C7. Elemental Analysis: C 47 H 31N3; Calc. C, 88.51 ; H, 4.90; N, 6.59; Found C, 88.63; H, 4.89; N, 6.81. LC-MS: Obs. 638.58 ([M+H] + ), exact mass: 637.25.

[0152] Example 14: Synthesis of compound 164

[0153]

[0154] Compound 164 was prepared according to the procedure described for the synthesis of compound 2 in Example 1, except that intermediate F13 was used instead of intermediate F5 and intermediate Cl instead of intermediate C7. Elemental Analysis: C 47 H 31 N3; Calc. C, 88.51 ; H, 4.90; N, 6.59; Found C, 88.63; H, 4.89; N, 6.81. LC-MS: Obs. 638.58 ([M+H] + ), exact mass: 637.25.

[0155] Example 15: Synthesis of compound 182

[0156]

[0157] Compound 182 was prepared according to the procedure described for the synthesis of compound 2 in Example 1, except that intermediate Fl was used instead of intermediate F5. Elemental Analysis: C 47 H 31 N3; Calc. C, 88.51 ; H, 4.90; N, 6.59; Found C, 88.63; H, 4.89; N, 6.81. LC-MS: Obs. 638.58 ([M+H] + ), exact mass: 637.25.

[0158] Example 16: Synthesis of compound 197

[0159]

[0160] Compound 197 was prepared according to the procedure described for the synthesis of compound 2 in Example 1, except that intermediate F2 was used instead of intermediate F5. Elemental Analysis: C 53 H 35 N3; Calc. C, 88.51 ; H, 4.90; N, 6.59; Found C, 88.63; H, 4.89; N, 6.81. LC-MS: Obs. 638.58 ([M+H] + ), exact mass: 637.25.

[0161] Example 17: Synthesis of compound 242

[0162]

[0163] Compound 242 was prepared according to the procedure for synthesis of compound 2 in Example 1, except that intermediate F4 was used instead of intermediate F5. Elemental Analysis: C 51 H 33 N3; Calc: C, 89.05; H, 4.84; N, 6.11; Found: C, 89.16; H, 4.97; N, 5.87. LC-MS: Found: 688.41 ([M+H] + ), Exact Mass: 687.27.

[0164] Example 18: Synthesis of compound 257

[0165]

[0166] Compound 257 was prepared according to the procedure for synthesis of compound 2 in Example 1, except that intermediate F3 was used instead of intermediate F5. Elemental Analysis: C 51 H 33 N3; Calc: C, 89.05; H, 4.84; N, 6.11; Found: C, 88.99; H, 4.95; N, 6.06. LC-MS: Found: 688.18 ([M+H] + ), Exact Mass: 687.27.

[0167] Example 19: Synthesis of compound 271

[0168]

[0169] Compound 271 was prepared according to the procedure for synthesis of compound 2 in Example 1, except that intermediate F14 was used instead of intermediate F5. Elemental Analysis: C 45 H 29 N5; Calc: C, 84.48; H, 4.57; N, 10.95; Found: C, 84.45; H, 4.52; N, 11.02. LC-MS: Found: 640.35 ([M+H] + ), Exact Mass: 639.24.

[0170] Example 20: Synthesis of compound 274

[0171]

[0172] Compound 276 was prepared according to the procedure for the synthesis of Compound 2 in Example 1, except that intermediate F15 was used in place of intermediate F5, and intermediate Cl was used in place of intermediate C7. Elemental Analysis: C 45 H 29 N5; Calc: C, 84.48; H, 4.57; N, 10.95; Found: C, 84.43 H, 4.58; N, 10.97. LC-MS: Found: 640.40 ([M+H] + ), Accurate Mass: 639.24.

[0173] II. Device Preparation Examples

[0174] The application effects of the compounds synthesized according to the present application as electron transport layers in devices are illustrated in detail below through Device Examples 1-20 and Device Comparative Examples 1-10. Device Examples 1-20 and Device Comparative Examples 1-10 have the same device manufacturing process as Device Example 1, and the same substrate material and electrode material are used, and the film thickness of the electrode material is also kept consistent, the only difference being that the electron transport material in the devices is changed. The device stack structure is shown in Table 3, and the performance test results of each device are shown in Table 4.

[0175] The molecular structures of the relevant materials are shown below:

[0176]

[0177]

[0178] The structures of comparative compounds ET-1, ET-2, ET-3, ET-4, ET-5, ET-6, ET-7, ET-8, ET-9 and ET-10 are shown above. The above materials are all commercially available.

[0179] Device Example 1

[0180] The specific preparation process is as follows:

[0181] As Figure 1As shown, the transparent substrate layer 1 is transparent glass, the anode layer 2 is Ag (100 nm), and the anode layer 2 is washed, i.e., sequentially washed with alkali, pure water, dried, and then washed with ultraviolet-ozone to remove organic residues on the surface of the anode layer. After the above washing, a hole injection layer 3 is formed on the anode layer 2 by using a vacuum evaporation device to evaporate HT-1 and P-1 with a film thickness of 10 nm, and the mass ratio of HT-1 to P-1 is 97:3. Then, HT-1 with a thickness of 117 nm is evaporated as a hole transport layer 4. Subsequently, EB-1 with a thickness of 10 nm is evaporated as an electron blocking layer 5. After the above electron blocking material is evaporated, an emitting layer 6 of the OLED light-emitting device is formed, which includes BH-1 as a host material and BD-1 as a dopant material, and the doping ratio of the dopant material is 3% by weight, and the film thickness of the emitting layer is 20 nm. After the above emitting layer 6, HB-1 is continuously evaporated with a film thickness of 8 nm as a hole blocking layer 7. On the above hole blocking layer 7, compound 2 and Liq are continuously evaporated with a mass ratio of 1:1. The vacuum evaporation film thickness of the material is 30 nm, which is an electron transport layer 8. On the electron transport layer 8, a LiF layer with a film thickness of 1 nm is formed by a vacuum evaporation device, which is an electron injection layer 9. On the electron injection layer 9, an Mg:Ag electrode layer with a film thickness of 16 nm is formed by a vacuum evaporation device, and the mass ratio of Mg to Ag is 1:9, which is a cathode layer 10. On the cathode layer 10, CP-1 with a thickness of 65 nm is vacuum evaporated as a CPL layer 11.

[0182] Device Examples 2-20 and Comparative Device Examples 1-10 are prepared in a similar manner to Device Example 1, and the substrate is transparent glass, and the anode is Ag (100 nm), and the difference is that the parameters in Table 3 below are used.

[0183] Table 3

[0184]

[0185]

[0186]

[0187] III. Device Test Examples

[0188] The devices prepared in II are tested for driving voltage, current efficiency, CIEy, and LT95 lifetime. The voltage, current efficiency, and CIEy are tested using an IVL (current-voltage-luminance) test system (Suzhou Fudashan Scientific Instrument Co., Ltd.), and the current density during testing is 10 mA / cm 2LT95 refers to the time for the luminance of the device to decay to 95% of the initial luminance, the current density during the test is 50 mA / cm 2 ; the lifetime test system is OLED device lifetime tester EAS-62C of Japan System Engineering Co., Ltd.; the high-temperature lifetime test temperature is 85℃, and LT80 refers to the time for the luminance of the device to decay to 80% under a specific luminance. The test results are shown in Table 4 below.

[0189] Table 4

[0190]

[0191]

[0192] As can be seen from the device test data results in Table 4 above, compared with the comparative devices using ET-1, ET-2, ET-3, ET-4, ET-5, ET-6, ET-7, ET-8, ET-9 and ET-10 as the electron transport layer material, the device prepared using the compound of the present application as the electron transport layer material has a significantly reduced driving voltage, while the current efficiency is improved, and the device lifetime is prolonged, for example, the lifetime is substantially 1.15 times or more of the comparative devices 1-7.

[0193] The structural formulas of the comparative compounds ET-1, ET-2, ET-3, ET-4, ET-5, ET-6, ET-7, ET-8, ET-9 and ET-10 used in the comparative examples are close to the present application, only some slight differences, such as only through the change of the intermediate bridging group, or the change of the triazine and phenanthryl group at the connecting site of the bridging group, however, unexpectedly, the compound of the present application as the electron transport material achieves better technical effect than the comparative compounds.

[0194] The above only describes the preferred embodiments of the present application, and is not intended to limit the present application, any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A compound containing a triazine and phenanthrene structure, characterized in that, The structure of the compound is shown in any one of general formulas (1-1) to (1-3): In general formulas (1-1) to (1-3), R1 represents phenyl, naphthyl, or biphenyl; Z1 and Z2 are represented independently as CH or N atoms; Z3 is represented as CH.

2. The compound containing triazine and phenanthrene structures according to claim 1, characterized in that, The structure of the compound is shown in any one of general formulas (2-1) to (2-9): In general formulas (2-1) to (2-9), R1 has the same meaning as defined in claim 1; the connection sites of phenanthrene and other groups are L1, L2, L3, L4 or L5.

3. The compound containing triazine and phenanthrene structures according to claim 1, characterized in that, The structure of the compound is shown in any one of general formulas (3-1) to (3-9): In general formulas (3-1) to (3-9), the meaning of R1 is the same as that in claim 1.

4. The compound containing triazine and phenanthrene structures according to claim 1, characterized in that, R1 represents phenyl.

5. The compound containing triazine and phenanthrene structures according to claim 1, characterized in that, R1 represents biphenyl.

6. The compound containing triazine and phenanthrene structures according to claim 1, characterized in that, R1 represents naphthyl.

7. The compound containing triazine and phenanthrene structures according to claim 1, characterized in that, The specific structure of the compound is any one of the following structures:

8. An organic electroluminescent device, comprising a first electrode and a second electrode, wherein a multilayer organic thin film layer is disposed between the first electrode and the second electrode, characterized in that, At least one organic thin film layer contains the compound containing triazine and phenanthrene structures as described in any one of claims 1 to 7.

9. The organic electroluminescent device according to claim 8, characterized in that, The organic thin film layer includes an electron transport layer containing a compound containing a triazine and phenanthrene structure as described in any one of claims 1 to 7.

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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