A triazine-containing compound and an organic electroluminescent device thereof

Abstract

The application discloses a triazine-containing compound and an organic electroluminescent device thereof, and belongs to the technical field of semiconductor materials. The structure of the compound is shown in general formula (1): the triazine-containing compound is applied to an organic thin film layer of an organic electroluminescent device. The triazine-containing compound has good stability and electronic resistance, and has good electronic injection and electronic transmission capacity. When the compound is used as a material of the organic electroluminescent device, the driving voltage of the device is significantly reduced, and the service life of the device is significantly improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of semiconductor materials, and particularly relates to a triazine-containing compound and an organic electroluminescent device thereof. 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. The organic electroluminescent 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 organic electroluminescent device. As a current device, when a voltage is applied to the electrodes of the organic electroluminescent device, and the positive and negative charges in the organic layer functional material film layer are acted on by the electric field, the positive and negative charges are further recombined in the light-emitting layer, that is, the organic electroluminescence is generated.

[0003] At present, OLED display technology has been applied in the fields of smart phones, tablet computers, televisions and the like, but compared with the actual product application requirements, the performance of the organic electroluminescent device such as luminous efficiency and service life still needs to be further improved. In order to continuously improve the performance of the organic electroluminescent device, the organic optoelectronic functional material needs to be continuously researched and innovated, and a higher performance organic optoelectronic functional material needs to be created.

[0004] The organic optoelectronic functional material applied to the organic electroluminescent device can be divided into two categories in terms of use, which are charge injection and transport material and light-emitting material. Further, the charge injection and transport material can be divided into electron injection and transport material, electron blocking material, hole injection and transport material, and hole blocking material. As a charge transport material, it is required to have good carrier mobility, high glass transition temperature and the like. For the organic electroluminescent device, 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 capacity 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 capacity and high durability of electrons.

[0005] For the device lifetime, the heat resistance and film stability of the material are also important, the material with low heat resistance is not only easy to produce decomposition when the material is evaporated, but also the heat produced by the device during the device working will produce thermal decomposition, thus causing the material deterioration. In the case of poor material film phase stability, the material also occurs thin film crystallization in a short time, causing the organic film layer to directly produce layer separation, resulting in device deterioration. Therefore, the material used is required to have high heat resistance and good film stability.

[0006] With the demand for improving the performance of organic electroluminescent devices, the requirement for material performance is also increasing, not only requires good material stability, and needs to achieve good efficiency and lifetime at low driving voltage. However, the current electron transport material has insufficient heat resistance and stability, and the material has defects in electron resistance, which causes the material to separate or decompose during the device working, thus resulting in short device lifetime. SUMMARY

[0007] In view of the above problems existing in the prior art, the applicant of the present application provides a triazine-containing compound and an organic electroluminescent device thereof. The triazine-containing compound of the present application is connected by a specific phenyl bridging group, 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 prolong the working life of the device.

[0008] A triazine-containing compound, the structure of the compound is shown in general formula (1):

[0009]

[0010] In general formula (1), R1, R2, R3 and R4 represent hydrogen atoms, phenyl groups substituted or unsubstituted by Ra;

[0011] and only one of R1, R2, R3 and R4 represents a phenyl group substituted or unsubstituted by Ra;

[0012] R5 represents a structure shown in general formula (2);

[0013] Ar1 and Ar2 each independently represent a phenyl group substituted or unsubstituted by Rb, a naphthyl group substituted or unsubstituted by Rb, a biphenyl group substituted or unsubstituted by Rb, a terphenyl group substituted or unsubstituted by Rb, a pyridyl group substituted or unsubstituted by Rb, and a pyrimidyl group substituted or unsubstituted by Rb;

[0014] Ar1 and Ar2 can be the same or different;

[0015] Ar3, Ar4 represents phenyl substituted or unsubstituted by Rc, naphthyl substituted or unsubstituted by Rc, biphenyl substituted or unsubstituted by Rc, terphenyl substituted or unsubstituted by Rc, pyridyl substituted or unsubstituted by Rc, pyrimidyl substituted or unsubstituted by Rc;

[0016] Ar3, Ar4 can be the same or different;

[0017] Ra represents phenyl, biphenyl, terphenyl, pyridyl, pyrimidyl;

[0018] Rb represents cyano, phenyl, biphenyl, terphenyl, pyridyl, pyrimidyl;

[0019] Rc represents phenyl, biphenyl, terphenyl, pyrimidyl;

[0020] The connection site of R5 is L1, L2 or L3, and the connection site of R4 is L1, L2, L3, L4 or L5;

[0021] The connection site of R5 is L1, and the connection site of R4 is L2, L3, L5;

[0022] The connection site of R5 is L2, and the connection site of R4 is L1, L3, L4, L5;

[0023] The connection site of R5 is L3, and the connection site of R4 is L1, L2, L4, L5;

[0024] And when the connection site of R5 is L3, and the connection site of R4 is L1 or L5, Ar3 does not represent naphthyl or biphenyl.

[0025] Further, the structure of the compound is as shown in any one of general formula (2-1) to general formula (2-2):

[0026]

[0027] In general formula (2-1) to general formula (2-2), Ar1, Ar2, Ar3, Ar4, R1, R2, R3, R4 have the same meaning as defined in general formula (1) and general formula (2) above.

[0028] Further, the structure of the compound is as shown in any one of general formula (2-3) to general formula (2-5):

[0029]

[0030] In general formula (2-3) to general formula (2-5), Ar1, Ar2, Ar3, Ar4, R1, R2, R3, R4 have the same meaning as defined in general formula (1) and general formula (2) above.

[0031] Further, the structure of the compound is shown as any one of general formula (2-6) to general formula (2-8):

[0032]

[0033] In general formula (2-6) to general formula (2-8), the meanings of Ar1, Ar2, Ar3, Ar4, R1, R2, R3, R4 are the same as defined in general formula (1) and general formula (2) above.

[0034] Further, the structure of the compound is shown as any one of general formula (3-1) to general formula (3-11):

[0035]

[0036] In general formula (3-1) to general formula (3-11), the meanings of Ar1, Ar2, Ar3, Ar4, R1, R2, R3, R4 are the same as defined in general formula (1) and general formula (2) above.

[0037] Further, the Ar1, Ar2 are independently represented as any one of

[0038]

[0039]

[0040] The Ar3, Ar4 are independently represented as:

[0041]

[0042] any one of

[0043] Further, the structure of the compound is shown as general formula (3-10):

[0044] The Ar1 is independently represented as The Ar2 is independently represented as:

[0045]

[0046] any one of

[0047] The Ar3, Ar4 are independently represented as: any one of

[0048] ​Further, the specific structure of the compound is any one of the following structures:

[0049]

[0050]

[0051]

[0052]

[0053]

[0054]

[0055]

[0056] The application further discloses an organic electroluminescent device, comprising a substrate, a first electrode and a second electrode, wherein a plurality of organic thin film layers are arranged between the first electrode and the second electrode, and the organic thin film layers contain the triazine-containing compound.

[0057] Further, the organic thin film layers comprise a hole transport region thin film layer, a light-emitting region thin film layer and an electron transport region thin film layer, and the electron transport region thin film layer contains the triazine-containing compound.

[0058] Further, the electron transport region thin film layer comprises an electron transport layer, and the electron transport layer contains the triazine-containing compound.

[0059] Further, the hole transport region thin film layer comprises a hole injection layer, a hole transport layer and an electron blocking layer, the electron transport region thin film layer comprises a hole blocking layer, an electron transport layer and an electron injection layer, and the electron transport layer contains the triazine-containing compound.

[0060] The application further discloses a display device, which contains the organic electroluminescent device.

[0061] Technical effects

[0062] The compound of the application is based on a double-triazine structure and is connected through a specific bridging group, and the compound has good electron resistance and stability, and has good electron injection and transport capacity.

[0063] The compound of the application has strong anti-electron properties, which can effectively improve the electron stability of the material. In addition, the specific connection mode of the compound of the application can increase the weak interaction in the molecule, effectively reduce the evaporation temperature of the molecule, and improve the thermal durability of the material.

[0064] The specific connection mode of the compound can inhibit intermolecular π-π stacking, significantly improve the electron mobility of the molecule, and reduce the driving voltage of the device. In addition, the glass transition temperature of the material can be improved, and the thin film stability of the material can be effectively improved. Therefore, the device driving voltage can be effectively reduced, the device efficiency and service life can be improved.

[0065] The compound can easily make the lithium ion in the lithium complex be reduced and be free under the action of electric field or heat energy due to the strong electricity absorption conjugation effect, so as to improve the electron injection capacity. Therefore, the compound has excellent electron transport capacity and good electron injection property as an electron transport material, and can effectively reduce the device driving voltage, improve the device efficiency and service life. BRIEF DESCRIPTION OF DRAWINGS

[0066] Figure 1 The structure schematic diagram of the material listed in the application applied to the OLED device is shown in the figure. 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 light extraction layer.

[0067] Figure 2 The nuclear magnetic hydrogen spectrum diagram of compound 1 in deuterated reagent CDCl3 is shown in the figure.

[0068] Figure 3 The nuclear magnetic hydrogen spectrum diagram of compound 203 in deuterated reagent CDCl3 is shown in the figure.

[0069] Figure 4 The nuclear magnetic hydrogen spectrum diagram of compound 213 in deuterated reagent CDCl3 is shown in the figure.

[0070] Figure 5 The nuclear magnetic hydrogen spectrum diagram of compound 217 in deuterated reagent CDCl3 is shown in the figure. DETAILED DESCRIPTION

[0071] The technical solutions of the application will be described in detail below in combination with the embodiments.

[0072] In the drawings, the size of the 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.

[0073] In the present application, the words indicating the orientation such as "upper" and "lower" used in describing the electrode and the organic electroluminescent device, and other structures, only indicate the orientation in a certain specific state, and do not mean that the related structure can only exist in the described orientation; on the contrary, if the structure can be transformed, for example, inverted, the orientation of the structure is changed accordingly. Specifically, in the present application, the "lower" side of the electrode refers to the side of the electrode that is close to the substrate during the preparation process, and the opposite side away from the substrate is the "upper" side.

[0074] Organic electroluminescent device

[0075] The organic electroluminescent device of the present application can be a bottom-emitting organic electroluminescent device, a top-emitting organic electroluminescent device, and a stacked organic electroluminescent device, without specific limitation.

[0076] The organic electroluminescent device of the present application includes a substrate, a first electrode, a multilayer organic thin film layer, and a second electrode. Among them, the multilayer organic thin film layer includes a hole transport region, a light-emitting layer, and an electron transport region, the hole transport region includes a hole injection layer, a hole transport layer, and an electron blocking layer, the electron transport region includes a hole blocking layer, an electron transport layer, and an electron injection layer, and in addition, a cover layer can be provided on the second electrode.

[0077] The layers that can be contained in the organic electroluminescent device of the present application and the positional relationship of each layer are as follows: a substrate, a first electrode, a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a second electrode can be contained, and if the above layers exist, among them, the first electrode is on the substrate, the hole injection layer is on the first electrode, 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 electron blocking layer, the hole blocking layer is on the light-emitting layer, the electron transport layer is on the hole blocking layer, the electron injection layer is on the electron transport layer, the second electrode is on the electron injection layer, and the cover layer is on the second electrode.

[0078] As the substrate of the organic electroluminescent device of the present application, any substrate commonly used for organic electroluminescent devices can be used. Examples are transparent substrates such as glass or transparent plastic substrates; opaque substrates such as silicon substrates; flexible PI film substrates. Different substrates have different mechanical strength, thermal stability, transparency, surface smoothness, and water resistance. Depending on the properties of the substrate, its use direction is different. In the present application, it is preferred to use a transparent substrate, and the thickness of the substrate is not particularly limited.

[0079] A first electrode can be formed on a substrate, and the first electrode and a second electrode can face each other. The first electrode can be an anode or a cathode. In the present application, the first electrode serves as an anode, and the anode material is preferably a material having a high work function so that holes are easily injected into an 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 including two or more layers. 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.

[0080] A hole injection layer, a hole transport layer, and an electron blocking layer can be disposed between the first electrode and the light-emitting layer.

[0081] The hole injection layer can include a host material and a P-type dopant material. The host material can be selected from conventional hole transport materials in the art, and is preferably the same organic material as the hole transport layer. The P-type dopant material is a compound having charge conductivity disclosed in the art, and can be selected from the compounds disclosed in the following patent documents: WO2011073149A, EP1968131A1, EP2276085A1, EP2213662A1, EP1722602A1, EP2045848A1, DE102007031220A1, US20100181555A1, US20100102709A1, WO2009003455A1, WO2010094378A1, WO2011120709A1, US20100096600A1, DE102012209523A1, CN101728485A, and WO2012095143A1, but is not limited thereto.

[0082] For example, the following compounds:

[0083]

[0084] According to the present application, P1 is preferably used as the P-type dopant material.

[0085] The thickness of the hole injection layer of the present application can be 1-100 nm, preferably 2-50 nm, and more preferably 5-20 nm.

[0086] The material of the hole transport layer is preferably a material having a high hole mobility, which enables holes to be transferred from the anode or the hole injection layer to the light-emitting layer.

[0087] Preferably, as the hole transport layer material of the present application, a compound disclosed in the following prior art can be optionally selected:

[0088]

[0089] The thickness of the hole transport layer of the present application can be 5-200 nm, preferably 10-180 nm, and more preferably 20-150 nm.

[0090] 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 play a role in blocking the energy loss of the light emitting layer material; the HOMO energy level of the electron blocking layer material is between the HOMO energy level of the hole transport layer material and the HOMO energy level of the light emitting layer host material, which is conducive to the injection of holes from the positive electrode into the light emitting layer, while the electron blocking layer material requires 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 electron blocking, 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.

[0091] In an embodiment of the present application, as the electron blocking layer material of the present application, a compound disclosed in the following prior art can be optionally selected:

[0092]

[0093] According to the present application, the thickness of the electron blocking layer can be 1-200 nm, preferably 5-150 nm, and more preferably 5-50 nm.

[0094] According to the present application, the light emitting layer is located between the electron blocking layer and the hole blocking layer, and 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 of an anthracene derivative, a quinoxaline derivative, a triazine derivative, an xanthone derivative, a benzophenone derivative, a carbazole derivative, a pyridine derivative, or a pyrimidine derivative, or a combination of two thereof. The guest material can be a pyrene derivative, a boron derivative, a fluorene derivative, a spirofluorene derivative, an iridium complex, or a platinum complex.

[0095] The thickness of the light emitting layer of the present application can be 5-60 nm, preferably 10-50 nm, and more preferably 20-45 nm.

[0096] A hole blocking layer can be disposed on the light emitting layer. The triplet (T1) energy level of the hole blocking layer material is 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.

[0097] As the hole blocking layer of the organic electroluminescent device of the present application, the hole blocking layer materials for organic electroluminescent devices disclosed in the following prior art can be used:

[0098]

[0099] The thickness of the hole blocking layer of the present application can be 2-200 nm, preferably 5-150 nm, and more preferably 5-50 nm, but the thickness is not limited to this range.

[0100] 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 comprises one or more organic compounds of the present application. Preferably, the electron transport layer consists of the organic compounds of the present application and other electron transport layer materials. More preferably, the other electron transport layer materials are electron transport materials commonly used in the art. Most preferably, the electron transport layer consists of the organic compounds of the present application and Liq, and the ratio of the organic compounds of the present application and the other electron transport layer materials is 1:9-9:1, preferably 2:8-8:2, more preferably 4:6-6:4, and most preferably 5:5.

[0101] 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.

[0102] According to the present application, an electron injection layer can be disposed between the electron transport layer and the cathode. The electron injection layer material is generally a material having a low work function, preferably, so that electrons are easily injected into the organic functional material layer. Preferably, the electron injection layer material is an N-type metal material. As the electron injection layer material of the organic electroluminescent device of the present application, the electron injection layer materials for organic electroluminescent devices disclosed in the following prior art can be used: LiF, Cs2CO3, CsF, Csq, NaF, MgF2, CaF2, Al2O3, Yb.

[0103] The thickness of the electron injection layer of the present application can be 0.1 to 5 nm, preferably 0.5 to 3 nm, and more preferably 0.8 to 1.5 nm, but the thickness is not limited to this range.

[0104] According to the present application, as previously described, the second electrode can be a cathode or an anode. In the present application, the second electrode is used as a cathode. The material used to form the cathode can be a material having a low work function, such as a metal, an alloy, a conductive compound, or a mixture thereof. Non-limiting examples of the cathode material can include lithium (Li), ytterbium (Yb), magnesium (Mg), aluminum (Al), calcium (Ca), and aluminum-lithium (Al-Li), magnesium-indium (Mg-In), and magnesium-silver (Mg-Ag). The thickness of the cathode depends on the material used, and is typically 5 to 100 nm, preferably 7 to 50 nm, and more preferably 10 to 25 nm.

[0105] Optionally, in order to improve the light extraction efficiency of the organic electroluminescent device, a light extraction layer (i.e., a CPL layer) can also be added on the second electrode (i.e., the cathode) of the device. The following compounds disclosed in the art in the prior art can be used as the CPL layer material.

[0106]

[0107]

[0108] The thickness of the CPL layer is typically 5 to 300 nm, preferably 20 to 100 nm, and more preferably 40 to 80 nm.

[0109] The organic electroluminescent device can also include an encapsulation structure. The encapsulation structure can be a protective structure that prevents external substances, such as moisture and oxygen, from entering the organic layer of the organic electroluminescent device. The encapsulation structure can be, for example, a can, such as a glass can or a metal can, or a thin film covering the entire surface of the organic layer.

[0110] Method of manufacturing an organic electroluminescent device

[0111] The method of manufacturing the above-described organic electroluminescent device of the present application includes sequentially laminating a first electrode, a multi-layer organic thin film layer, and a second electrode on a substrate. Herein, the multi-layer organic thin film layer is formed by sequentially laminating a hole transport region, i.e., a hole injection layer, a hole transport layer, and an electron blocking layer, on the first electrode from bottom to top, a light-emitting layer, and an electron transport region, i.e., a hole blocking layer, an electron transport layer, and an electron injection layer, on the light-emitting layer from bottom to top. In addition, optionally, a CPL layer can also be laminated on the second electrode to improve the light extraction efficiency of the organic electroluminescent device.

[0112] As for the lamination, a method such as vacuum deposition, vacuum evaporation, spin coating, casting, LB method, inkjet printing, laser printing or LITI, but not limited thereto, can be used. Among them, the vacuum evaporation means that the material is heated and plated on the substrate in a vacuum environment.

[0113] In the present application, it is preferable to use a vacuum evaporation method to form the respective layers, wherein the vacuum evaporation can be performed at a temperature of about 100-500°C, at a rate of about 10 -8 -10 -2 Torr and at a rate of about 10 -6 -10 -2 Torr, more preferably 10 -5 -10 -3 Torr. The rate is about more preferably about

[0114] In addition, it should be noted that the materials used to form the respective layers in the present application can be used as a single layer by being formed into a film alone, can be used as a single layer by being formed into a film after being mixed with other materials, and can be a stacked structure between layers formed into a film alone, a stacked structure between layers formed into a film after being mixed, or a stacked structure of layers formed into a film alone and layers formed into a film after being mixed.

[0115] Display device

[0116] The present application also relates to a display device, particularly a flat panel display device, comprising the above-described organic electroluminescent device. In a preferred embodiment, the display device can comprise one or more of the above-described organic electroluminescent devices, and in the case of comprising a plurality of devices, the devices are combined in a lateral or longitudinal stack. The display device can further comprise at least one thin film transistor. The thin film transistor can comprise 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 comprise crystalline silicon, amorphous silicon, an organic semiconductor, or an oxide semiconductor, but it is not limited thereto.

[0117] Exemplary embodiments have been disclosed herein, although specific terminology has been employed, such terminology is for the purpose of describing and not for the purpose of limiting. In some instances, features, attributes and / or benefits can be utilized in combinations that are not specifically stated in the specification. In some instances, features, attributes and / or benefits can be utilized alone or in combinations with other features, attributes and / or benefits. Accordingly, the skilled artisan understands that where particular embodiments have been described in the context of a particular embodiment, that the features, attributes and / or benefits described can be utilized in other embodiments as well. Accordingly, the skilled artisan will appreciate that the foregoing description is by way of example only, and is not intended to limit the application solely thereto. Rather, it is intended that the scope of the present application be defined by the appended claims and equivalents.

[0118] The following examples are intended to better illustrate the application and are not intended to limit the scope of the application.

[0119] Examples

[0120] I. Preparation of compounds

[0121] The starting materials involved in the synthesis examples of the present application can be purchased from the market or prepared by conventional preparation methods in the art;

[0122] Preparation of intermediate E1:

[0123]

[0124] In a round-bottom flask, under nitrogen protection, raw material C3 (2.7 g, 10 mmol), raw material D1 (5.2 g, 12 mmol), KOAc (2.9 g, 30 mmol), tetrahydrofuran (100 mL), water (30 mL) were added in turn, the air was replaced by nitrogen for 30 min, Pd(dppf)Cl2(0.06 g, 0.08 mmol), 2-dicyclohexylphosphine-2',4',6'-triisopropyl biphenyl (0.06 g, 0.13 mmol) were added, and heated to reflux under nitrogen protection for 15 h. TLC detection of the reaction liquid showed that raw material C3 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 80 mL of dichloromethane, 100 mL of water was added for washing, poured into a separatory funnel, shaken and then allowed to stand to separate the layers, the aqueous phase was extracted with dichloromethane (30 mL*3), the organic phase was combined and dried with anhydrous magnesium sulfate, filtered, the filtrate was rotary evaporated to remove dichloromethane to obtain a crude product, which was purified by silica gel column chromatography to obtain intermediate E1. LC-MS: measured value: 496.22 ([M+H] + ), accurate mass: 495.15.

[0125]

[0126] In a round-bottom flask, under nitrogen protection, intermediate F1 (1.2 g, 3 mmol), pinacol diborane (0.8 g, 3.3 mmol), KOAC (0.9 g, 9 mmol), dioxane (20 mL), nitrogen was replaced for 40 min, Pd(PPh3)4(0.07 g, 0.06 mmol) was added, and heated to reflux for 15 h under nitrogen protection. The reaction liquid was detected by TCL, and it was found that intermediate F1 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, and the aqueous phase was extracted with dichloromethane (30 mL*3). The organic phase was combined, dried with anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by rotary evaporation to obtain intermediate G1. LC-MS: measured value: 385.21 ([M+H] + ); accurate mass: 384.18.

[0127]

[0128] Other intermediate G2 was prepared by the same synthetic method of intermediate G1, except that intermediate F1 was replaced by intermediate E10.

[0129] LC-MS: measured value: 461.09 ([M+H] + ); accurate mass: 460.21.

[0130]

[0131] Other intermediate G3 was prepared by the same synthetic method of intermediate G1, except that intermediate F1 was replaced by intermediate E11.

[0132] LC-MS: measured value: 537.15 ([M+H] + ); accurate mass: 536.24.

[0133] Other intermediate E was prepared by the same synthetic method of intermediate E1, except that the raw materials were different, and the raw materials and intermediates used were as shown in Table 1;

[0134] Table 1

[0135]

[0136]

[0137]

[0138] Example 1: Synthesis of compound 1

[0139]

[0140] In a 500 mL round bottom flask, under nitrogen atmosphere, intermediate E1 (5.0 g, 10 mmol) and raw material D4 (4.7 g, 12 mmol) were completely dissolved in a mixed solution of toluene, water and ethanol with a volume ratio of 3:1:1, 150 mL, then 2M potassium carbonate solution (K2CO3) 100 mL was added, Pd(PPh3)4 (0.35 g, 0.30 mmol) was added, and then heated and stirred for 6 hours, then cooled to room temperature, the water layer was removed, dried with anhydrous magnesium sulfate, and then concentrated under reduced pressure, recrystallized with ethyl acetate 280 mL to obtain compound 1. Elemental analysis: C 48 H 32 N6 Theoretical value: C, 83.21; H, 4.66; N, 12.13; Test value: C, 83.16; H, 4.63; N, 12.17. LC-MS: Test value: 693.07 ([M+H] + ), accurate mass: 692.27.

[0141] Other compounds were prepared by the same synthesis method as compound 1, except that the intermediates and raw materials were different, and the raw materials and intermediates used are shown in Table 2.

[0142] Table 2

[0143]

[0144]

[0145]

[0146] II. Device preparation examples

[0147] The application effect of the compound synthesized according to the application as an electron transport material in a device is illustrated in detail below through device examples 1-27 and device comparison examples 1-13. Device examples 1-27 and device comparison examples 1-13 have the same device manufacturing process, and the same substrate material and electrode material are used, and the film thickness of the electrode material is also consistent, the difference is that the electron transport layer material in the device is changed. The device layer structure is shown in Table 3, and the performance test results of each device are shown in Table 4.

[0148] The molecular structure of the related material is as follows:

[0149]

[0150]

[0151] Comparative compounds ET-1, ET-2, ET-3, ET-4, ET-5, ET-6, ET-7, ET-8, ET-9, ET-10, ET-11, ET-12, ET-13 structures are shown above. All of the above materials are commercially available.

[0152] Device Comparative Example 1

[0153] The specific preparation process is as follows:

[0154] As shown in Figure 1 , the transparent substrate layer 1 is transparent glass, Ag (100 nm) is evaporated as an anode layer 2, on the anode layer 2, a vacuum evaporation device is used to evaporate HT-1 and P-1 with a film thickness of 10 nm as a hole injection layer 3, the mass ratio of HT-1 and P-1 is 97:3. Then HT-1 with a thickness of 130 nm is evaporated as a hole transport layer 4. Then 5 nm thick EB-1 is evaporated as an electron blocking layer 5. After the above-mentioned electron blocking material is evaporated, the light-emitting layer 6 of the OLED light-emitting device is prepared, BH-1 is used as the host material, BD-1 is used as the dopant material, the doping ratio of the dopant material is 3% by weight, and the film thickness of the light-emitting layer is 20 nm. After the above-mentioned light-emitting layer 6, HB-1 is continuously evaporated with a film thickness of 5 nm as a hole blocking layer 7. On the above-mentioned hole blocking layer 7, ET-1 and Liq are continuously evaporated, the mass ratio of ET-1 and Liq is 1:1. The vacuum evaporation film thickness of this 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 prepared 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 prepared by a vacuum evaporation device, the mass ratio of Mg and Ag is 1:9, which is a cathode layer 10. On the cathode layer 10, 65 nm of CP-1 is vacuum evaporated as a CPL layer 11.

[0155] Device Examples 1-27 and Device Comparative Examples 2-13 are prepared in a similar manner to Device Comparative Example 1, except that the electron transport layer materials in Table 3 below are used.

[0156] Table 3

[0157]

[0158]

[0159]

[0160]

[0161] III. Device Test Examples

[0162] The devices prepared in Example II were tested for driving voltage and LT95 lifetime. The voltage was tested using IVL (current-voltage-luminance) test system (Suzhou Fudashan Scientific Instrument Co., Ltd.), and the current density during the test was 10 mA / cm 2 . LT95 refers to the time for the luminance of the device to decay to 95% of the initial luminance, and the current density during the test was 30 mA / cm 2 ; the lifetime test system was EAS-62C type OLED device lifetime tester of Japan System Technological Research Co., Ltd.; the high temperature lifetime test temperature was 85℃, and LT95 refers to the time for the luminance of the device to decay to 95% of the initial luminance, and the current density during the test was 20 mA / cm 2 ;

[0163] The test results are shown in Table 4 below.

[0164] Table 4

[0165]

[0166]

[0167]

[0168] 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, ET-10, ET-11, ET-12, ET-13 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, and at the same time, the device lifetime is prolonged, for example, the lifetime is substantially 1.25 times or more than that of the comparative devices 1-13.

[0169] The above description is merely 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 triazine-containing compound, characterized in that, The structure of the compound is shown in general formula (3-10): In general formula (3-10), R4 represents a phenyl group that is substituted or unsubstituted with Ra; Ar1 represents phenyl, naphthyl, diphenyl, and triphenyl; Ar2 represents a phenyl group substituted with Rb, a naphthyl group substituted with Rb, a diphenyl group substituted with Rb, and a triphenyl group substituted with Rb. Ar3 and Ar4 represent phenyl groups with or without Rc substitution, naphthyl groups with or without Rc substitution, diphenyl groups with or without Rc substitution, and triphenyl groups with or without Rc substitution. Ar3 and Ar4 can be the same or different; Ra represents phenyl, diphenyl, and triphenyl; Rb represents cyano group; Rc represents phenyl, diphenyl, or triphenyl.

2. The triazine-containing compound according to claim 1, characterized in that, The Ar2 is represented as: any one of them; Ar1 is represented as: any one of them; Ar3 and Ar4 are represented independently as follows: Any one of them.

3. The triazine-containing compound according to claim 1, characterized in that, Ar1 is represented as The Ar2 is represented as: any one of them; Ar3 and Ar4 are represented independently as follows: Any one of them.

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

5. An organic electroluminescent device, comprising a substrate, 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, The organic thin film layer contains a triazine-containing compound as described in any one of claims 1 to 4.

6. An organic electroluminescent device according to claim 5, characterized in that, The organic thin film layer includes a hole transport region thin film layer, a light emission region thin film layer, and an electron transport region thin film layer, wherein the electron transport region thin film layer contains a triazine-containing compound as described in any one of claims 1 to 4.

7. The organic electroluminescent device according to claim 6, characterized in that, The electron transport region thin film layer includes an electron transport layer containing a triazine-containing compound as described in any one of claims 1 to 4.

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