WO2024066916A1 - Aromatic amine compound comprising quaterphenyl structure and organic electroluminescent device comprising same - Google Patents

Aromatic amine compound comprising quaterphenyl structure and organic electroluminescent device comprising same Download PDF

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WO2024066916A1
WO2024066916A1 PCT/CN2023/116380 CN2023116380W WO2024066916A1 WO 2024066916 A1 WO2024066916 A1 WO 2024066916A1 CN 2023116380 W CN2023116380 W CN 2023116380W WO 2024066916 A1 WO2024066916 A1 WO 2024066916A1
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unsubstituted
substituted
aromatic amine
amine compound
ring
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Chinese (zh)
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刘嵩远
魏天宇
张景
郑双权
徐凌伟
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石家庄诚志永华显示材料有限公司
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    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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Definitions

  • the present invention relates to the technical field of organic light-emitting semiconductors, and more specifically to an aromatic amine compound containing a quaternary phenyl structure and an organic electroluminescent device containing the same.
  • Organic electroluminescent devices are usually composed of a cathode, an electron injection layer, an electron transport layer, a light-emitting layer, a hole transport layer, a hole injection layer and an anode. Electrons and holes are injected from the cathode and anode respectively under an external electric field, and then move toward each other. Holes are transported to the light-emitting layer via the hole transport layer, and electrons are transported to the light-emitting layer via the electron transport layer. The electrons and holes that meet in the light-emitting layer recombine to form electron-hole pairs, i.e., excitons, and then the excitons radiate and transition to produce light emission.
  • electron-hole pairs i.e., excitons
  • the excitons generated in the light-emitting layer can easily diffuse to the hole transport layer interface or the hole transport layer side, which ultimately leads to light emission at the interface of the light-emitting layer or charge imbalance in the light-emitting layer, thereby emitting light at the interface of the hole transport layer, reducing the color purity and efficiency of the organic electroluminescent device, and ultimately leading to reduced luminous efficiency and shortened service life of the organic electroluminescent device. Improving the performance of the hole transport layer material or introducing a light-emitting auxiliary layer between the light-emitting layer and the hole transport layer can effectively avoid the above technical problems.
  • HOMO occupied molecular orbital
  • the light-emitting auxiliary layer has the function of assisting the hole transport layer and can block the electrons transferred from the cathode to confine the electrons in the light-emitting layer, increase the utilization rate of holes, and thus improve the luminous efficiency and life of the device.
  • hole transport layer materials and luminescent auxiliary layer materials generally have problems such as poor energy level and energy matching, resulting in a high driving voltage.
  • the commonly used technical means are to introduce rigid planar conjugated structures such as naphthalene, fluorene, and phenanthrene into the hole transport layer materials or luminescent auxiliary layer materials of organic electroluminescent devices. These structures have a large ⁇ electron cloud, which is conducive to reducing the device driving voltage, but such structures will deepen the degree of conjugation of organic molecules, resulting in a significant decrease in the T1 of the hole transport layer material or the luminescent auxiliary layer material.
  • the present invention provides an aromatic amine compound containing a quaternary phenyl structure and an organic electroluminescent device containing the same.
  • the aromatic amine compound not only has relatively high HOMO and LUMO energy levels and high T1, but also has high glass transition temperature and molecular thermal stability, and can be used as a hole transport layer material or a luminescent auxiliary layer material of an organic electroluminescent device, and can effectively reduce the driving voltage of the organic electroluminescent device, improve the efficiency of the device and extend the life of the device, thereby overcoming the defects of the prior art.
  • an aromatic amine compound containing a quaternary phenyl structure is provided, and the structural formula of the aromatic amine compound is shown in Formula I:
  • Ar 1 and Ar 2 are each independently selected from any one of a substituted or unsubstituted C 6 ⁇ C 60 aryl group, a substituted or unsubstituted C 5 ⁇ C 60 heteroaryl group, a substituted or unsubstituted C 10 ⁇ C 60 condensed ring aryl group, a substituted or unsubstituted C 9 ⁇ C 60 heterocondensed ring aryl group, and a substituted or unsubstituted C 3 ⁇ C 30 cycloalkyl group;
  • the substituent is selected from any one of deuterium, halogen, hydroxyl, cyano, nitro, amino, carboxyl or its salt, sulfonic acid or its salt , phosphate or its salt, C1-C10 alkyl, C6-C60 aryl, C5-C60 heteroaryl, C10 - C60 fused ring aryl , C9 - C60 heterofused ring aryl or C3 - C30 cycloalkyl, wherein
  • the two or more substituents may be the same or different and may be connected to form an aliphatic ring, an aromatic ring, a heteroaromatic ring, a condensed ring or a heterocondensed ring;
  • the L2 is selected from any one of a single bond, a substituted or unsubstituted C1 - C12 alkylene group, a substituted or unsubstituted C6 - C30 arylene group, and a substituted or unsubstituted C6 - C30 heteroarylene group;
  • Any hydrogen on the compound of formula I can be independently replaced by deuterium, alkyl or cycloalkyl.
  • R 1 and R 2 are each independently selected from any one of hydrogen, deuterium, substituted or unsubstituted C 1 to C 10 alkyl, substituted or unsubstituted C 3 to C 10 cycloalkyl, substituted or unsubstituted C 6 to C 30 aryl, substituted or unsubstituted C 5 to C 30 heteroaryl, substituted or unsubstituted C 1 to C 6 alkoxy, substituted or unsubstituted C 10 to C 60 condensed ring, substituted or unsubstituted C 9 to C 30 aralkyl, substituted or unsubstituted C 6 to C 30 aryloxy, substituted or unsubstituted C 6 to C 30 arylamine, and any two or more of the above groups can be connected to form an aliphatic ring, an aromatic ring, a heteroaromatic ring, a condensed ring or a heterocondensed ring;
  • the L1 is selected from any one of a single bond, O, S, a substituted or unsubstituted C1 - C12 alkylene group, and a substituted or unsubstituted C6 - C30 arylene group;
  • Any hydrogen on the compound represented by formula II can be independently replaced by deuterium, alkyl or cycloalkyl.
  • the compound represented by formula II is one of the structures represented by the following formula II-1 to formula II-7:
  • the L1 is selected from any one of a single bond, O, S, a substituted or unsubstituted C1 - C12 alkylene group, and a substituted or unsubstituted C6 - C30 arylene group;
  • the L2 is selected from any one of a single bond, O, and S;
  • the X is selected from any one of O, S, CR 3 R 4 and NR 5 ;
  • R 3 and R 4 are each independently selected from hydrogen, deuterium, substituted or unsubstituted C 1 to C 10 alkyl, substituted or unsubstituted substituted or unsubstituted C 6 ⁇ C 30 aryl group, substituted or unsubstituted C 5 ⁇ C 30 heteroaryl group, substituted or unsubstituted C 10 ⁇ C 60 condensed ring group, substituted or unsubstituted C 6 ⁇ C 30 aralkyl group, substituted or unsubstituted C 6 ⁇ C 30 aryloxy group, substituted or unsubstituted C 6 ⁇ C 30 arylthio group, R 3 and R 4 can be connected to each other to form an aliphatic ring, an aromatic ring, a heteroaromatic ring, a condensed ring or a heterocondensed ring;
  • the R 5 is selected from hydrogen, deuterium, substituted or unsubstituted C 1 to C 10 alkyl, substituted or unsubstituted C 6 to C 30 aryl;
  • Any hydrogen on the compounds represented by formula II-1 to formula II-7 can be independently replaced by deuterium, alkyl or cycloalkyl.
  • Ar2 is selected from any one of a substituted or unsubstituted C6 - C30 aryl group, a substituted or unsubstituted C5 - C30 heteroaryl group, a substituted or unsubstituted C10 - C30 condensed ring aryl group, a substituted or unsubstituted C9 - C30 heterocondensed ring aryl group, and a substituted or unsubstituted C3 - C15 cycloalkyl group.
  • Ar 2 is selected from any one of the following groups represented by a-1 to a-92:
  • the L2 is selected from a single bond, Any one of .
  • the compound represented by formula I is selected from any one of the following compounds:
  • the second aspect of the present invention provides use of the aromatic amine compound in an organic electroluminescent device.
  • the third aspect of the present invention provides an organic electroluminescent device, comprising an anode, a hole transport layer, a luminescence auxiliary layer, a luminescent layer, an electron transport region and a cathode arranged in sequence on a substrate; wherein the luminescence auxiliary layer and/or the hole transport layer comprises one or more aromatic amine compounds as described above.
  • the aromatic amine compound provided by the present invention has the following advantages with Formula I as the parent core: on the one hand, the parent core has a relatively large molecular weight, which can effectively improve the glass transition temperature and thermal stability of the aromatic amine compound; on the other hand, the 3rd position and the 5th position of the benzene connected to nitrogen are substituted by biphenyl and monophenyl respectively, and the biphenyl connected to the 3rd position is ortho-substituted.
  • connection in this special way can reduce the steric hindrance and improve the LUMO, energy gap value and T1 value of the aromatic amine compound;
  • the aromatic amine compound provided by the present invention is applied to the hole transport layer material or the light-emitting auxiliary layer of the organic electroluminescent device, and the energy level of the hole transport layer material or the light-emitting auxiliary layer material is more matched with the energy level of the adjacent organic layer.
  • the invention discloses a method for preparing an organic electroluminescent device having a hole transport layer material or a light-emitting auxiliary layer material, which can effectively reduce the driving voltage of the organic electroluminescent device;
  • the hole transport layer material or the light-emitting auxiliary layer material has a relatively high LUMO and energy gap value, which can block electrons or excitons from leaving the light-emitting layer, thereby improving the efficiency of the device;
  • the hole transport layer material or the light-emitting auxiliary layer material has a relatively high T1 value, and the energy transferred by the carriers of the hole transport layer or the light-emitting auxiliary layer can meet the light-emitting energy required for the transition of the light-emitting layer, thereby significantly improving the light-emitting efficiency of the organic electroluminescent device;
  • the hole transport layer material or the light-emitting auxiliary layer material has a high glass transition temperature and thermal stability, which can inhibit the evaporation and decomposition of the material and effectively improve the life of the
  • the preparation process of the compound of the present invention is simple and easy, the raw materials are easily available, and it is suitable for mass production and expansion.
  • FIG1 is a schematic structural diagram of an organic electroluminescent device containing an aromatic amine compound of the present invention
  • FIG2 shows the LOMO distribution diagram of the aromatic amine compound C1
  • FIG3 shows a triplet energy level orbital distribution diagram of the aromatic amine compound C1
  • FIG4 shows the LOMO distribution diagram of the aromatic amine compound C2
  • FIG5 shows a triplet energy level orbital distribution diagram of the aromatic amine compound C2
  • FIG6 shows the LOMO distribution diagram of the aromatic amine compound C3
  • FIG7 shows a triplet energy level orbital distribution diagram of the aromatic amine compound C3
  • FIG8 shows the LOMO distribution diagram of the aromatic amine compound C4
  • FIG9 shows a triplet energy level orbital distribution diagram of aromatic amine compound C4
  • FIG10 shows the LOMO distribution diagram of aromatic amine compound C29
  • FIG11 shows a triplet energy level orbital distribution diagram of aromatic amine compound C29
  • FIG12 shows the LOMO distribution diagram of aromatic amine compound C180
  • FIG13 shows a triplet energy level orbital distribution diagram of aromatic amine compound C180
  • FIG14 shows the LOMO distribution diagram of aromatic amine compound C216
  • FIG15 shows a triplet energy level orbital distribution diagram of aromatic amine compound C216
  • FIG16 shows the LOMO distribution diagram of aromatic amine compound C227
  • FIG17 shows the triplet energy level orbital distribution diagram of the aromatic amine compound C227.
  • the compounds of the present invention are suitable for use in light-emitting elements, display panels and electronic devices, and are particularly suitable for use in organic electroluminescent devices.
  • the electronic device of the present invention is a device comprising a layer of at least one organic compound, which may also comprise an inorganic material or a layer formed entirely of an inorganic material.
  • the electronic device is preferably an organic electroluminescent device (OLED), an organic integrated circuit (O-IC), an organic field effect transistor (O-FET), an organic thin film transistor (O-TFT), an organic light-emitting transistor (O-LET), an organic solar cell (O-SC), an organic dye-sensitized solar cell (O-DSSC), an organic optical detector, an organic photoreceptor, an organic field quenching device (O-FQD), a light-emitting electrochemical cell (LEC), an organic laser diode (O-laser) and an organic plasma emission device.
  • OLED organic electroluminescent device
  • OLED organic electroluminescent device
  • FIG. 1 The structural schematic diagram of an exemplary organic electroluminescent device is shown in Figure 1.
  • the aromatic amine compound of the present invention is prepared by using a representative reaction such as a Buchwald-Hartwig coupling reaction, a Suzuki coupling reaction or a Heck coupling reaction.
  • This embodiment provides an intermediate compound A, and the synthesis route of the compound is as follows:
  • the intermediate compound A used in the following examples was prepared in the above manner.
  • This embodiment provides an aromatic amine compound C-1, and the synthesis route of the aromatic amine compound is as follows:
  • This embodiment provides an aromatic amine compound C-2, and the synthesis route of the aromatic amine compound is as follows:
  • This embodiment provides an aromatic amine compound C-3, and the synthesis route of the aromatic amine compound is as follows:
  • This embodiment provides an aromatic amine compound C-4, and the synthesis route of the aromatic amine compound is as follows:
  • This embodiment provides an aromatic amine compound C-9, and the synthesis route of the aromatic amine compound is as follows:
  • Example 2 The method is the same as Example 1, except that B-9 (4.79 g, 10 mmol) replaces B-1, and the final product C-9 is 6.03 g (yield: 77%), MS (m/z) (M+): 783.
  • This embodiment provides an aromatic amine compound C-11, and the synthesis route of the aromatic amine compound is as follows:
  • Example 2 The method is the same as Example 1, except that B-11 (4.51 g, 10 mmol) replaces B-1, and the final product C-11 is 5.59 g (yield: 74%), MS (m/z) (M+): 755.
  • This embodiment provides an aromatic amine compound C-14, and the synthesis route of the aromatic amine compound is as follows:
  • Example 2 The method is the same as Example 1, except that B-14 (4.69 g, 10 mmol) replaces B-1, and the final product C-14 is 6.18 g (yield: 80%), MS (m/z) (M+): 773.
  • This embodiment provides an aromatic amine compound C-16, and the synthesis route of the aromatic amine compound is as follows:
  • Example 2 The method is the same as Example 1, except that A-16 (4.02 g, 10 mmol) replaces A, and B-16 (5.26 g, 10 mmol) replaces B-1, and finally the product C-16 is obtained: 6.01 g (yield: 71%), MS (m/z) (M+): 847.
  • This embodiment provides an aromatic amine compound C-17, and the synthesis route of the aromatic amine compound is as follows:
  • Example 2 The method is the same as Example 1, except that B-17 (5.75 g, 10 mmol) replaces B-1, and the final product C-17 is 6.68 g (yield: 76%), MS (m/z) (M+): 879.
  • This embodiment provides an aromatic amine compound C-20, and the synthesis route of the aromatic amine compound is as follows:
  • This embodiment provides an aromatic amine compound C-21, and the synthesis route of the aromatic amine compound is as follows:
  • Example 2 The method is the same as Example 1, except that B-21 (5.24 g, 10 mmol) replaces B-1, and finally the product C-21 is obtained: 5.80 g (yield: 70%), MS (m/z) (M+): 828.
  • This embodiment provides an aromatic amine compound C-22, and the synthesis route of the aromatic amine compound is as follows:
  • Example 2 The method is the same as Example 1, except that B-22 (5.73 g, 10 mmol) replaces B-1, and finally the product C-22 is obtained: 6.14 g (yield: 70%), MS (m/z) (M+): 877.
  • This embodiment provides an aromatic amine compound C-23, and the synthesis route of the aromatic amine compound is as follows:
  • Example 2 The method is the same as Example 1, except that B-23 (5.73 g, 10 mmol) replaces B-1, and finally the product C-23 is obtained: 7.19 g (yield: 82%), MS (m/z) (M+): 877.
  • This embodiment provides an aromatic amine compound C-26, and the synthesis route of the aromatic amine compound is as follows:
  • This embodiment provides an aromatic amine compound C-29, and the synthesis route of the aromatic amine compound is as follows:
  • Example 2 The method is the same as Example 1, except that B-29 (4.69 g, 10 mmol) replaces B-1, and finally the product C-29 is obtained: 6.34 g (yield: 82%), MS (m/z) (M+): 773.
  • This embodiment provides an aromatic amine compound C-31, and the synthesis route of the aromatic amine compound is as follows:
  • Example 2 The method is the same as Example 1, except that B-31 (5.40 g, 10 mmol) replaces B-1, and the final product C-31 is 6.75 g (yield: 80%), MS (m/z) (M+): 844.
  • This embodiment provides an aromatic amine compound C-52, and the synthesis route of the aromatic amine compound is as follows:
  • Example 2 The method is the same as Example 1, except that B-52 (5.26 g, 10 mmol) replaces B-1, and the final product C-52 is obtained: 6.14 g (yield: 74%), MS (m/z) (M+): 830.
  • This embodiment provides an aromatic amine compound C-53, and the synthesis route of the aromatic amine compound is as follows:
  • Example 2 The method is the same as Example 1, except that B-53 (5.33 g, 10 mmol) replaces B-1, and the final product C-53 is 6.53 g (yield: 78%), MS (m/z) (M+): 837.
  • This embodiment provides an aromatic amine compound C-73, and the synthesis route of the aromatic amine compound is as follows:
  • Example 2 The method is the same as Example 1, except that B-73 (4.95 g, 10 mmol) replaces B-1, and the final product C-73 is obtained: 6.07 g (yield: 76%), MS (m/z) (M+): 799.
  • This embodiment provides an aromatic amine compound C-84, and the synthesis route of the aromatic amine compound is as follows:
  • Example 2 The method is the same as Example 1, except that B-84 (5.76 g, 10 mmol) replaces B-1, and the final product C-84 is 7.13 g (yield: 81%), MS (m/z) (M+): 880.
  • This embodiment provides an aromatic amine compound C-111, and the synthesis route of the aromatic amine compound is as follows:
  • Example 2 The method is the same as Example 1, except that B-111 (3.61 g, 10 mmol) replaces B-1, and finally the product C-111 is obtained: 5.59 g (yield: 84%), MS (m/z) (M+): 666.
  • This embodiment provides an aromatic amine compound C-115, and the synthesis route of the aromatic amine compound is as follows:
  • Example 2 The method is the same as Example 1, except that B-115 (3.75 g, 10 mmol) replaces B-1, and finally the product C-115 is obtained: 5.44 g (yield: 80%), MS (m/z) (M+): 680.
  • This embodiment provides an aromatic amine compound C-121, and the synthesis route of the aromatic amine compound is as follows:
  • Example 2 The method is the same as Example 1, except that B-121 (3.71 g, 10 mmol) replaces B-1, and the final product C-121 is 5.67 g (yield: 84%), MS (m/z) (M+): 675.
  • This embodiment provides an aromatic amine compound C-131, and the synthesis route of the aromatic amine compound is as follows:
  • This embodiment provides an aromatic amine compound C-133, and the synthesis route of the aromatic amine compound is as follows:
  • Example 2 The method is the same as Example 1, except that B-133 (4.84 g, 10 mmol) is used to replace B-1, and the final product C-133 is 6.70 g (yield: 85%), MS (m/z) (M+): 788.
  • This embodiment provides an aromatic amine compound C-164, and the synthesis route of the aromatic amine compound is as follows:
  • Example 2 The method is the same as Example 1, except that B-164 (4.63 g, 10 mmol) replaces B-1, and the final product C-164 is 6.29 g (yield: 82%), MS (m/z) (M+): 767.
  • This embodiment provides an aromatic amine compound C-172, and the synthesis route of the aromatic amine compound is as follows:
  • Example 2 The method is the same as Example 1, except that B-172 (3.71 g, 10 mmol) replaces B-1, and the final product C-172 is 4.73 g (yield: 70%), MS (m/z) (M+): 675.
  • This embodiment provides an aromatic amine compound C-180, and the synthesis route of the aromatic amine compound is as follows:
  • Example 2 The method is the same as Example 1, except that B-180 (5.24 g, 10 mmol) is used to replace B-1, and the final product C-180 is 6.21 g (yield: 75%), MS (m/z) (M+): 828.
  • This embodiment provides an aromatic amine compound C-181, and the synthesis route of the aromatic amine compound is as follows:
  • Example 2 The method is the same as Example 1, except that B-181 (5.24 g, 10 mmol) replaces B-1, and the final product C-181 is 6.46 g (yield: 78%), MS (m/z) (M+): 828.
  • This embodiment provides an aromatic amine compound C-186, and the synthesis route of the aromatic amine compound is as follows:
  • Example 2 The method is the same as Example 1, except that B-186 (3.76 g, 10 mmol) is used to replace B-1, and the final product C-186 is 5.58 g (yield: 82%), MS (m/z) (M+): 680.
  • This embodiment provides an aromatic amine compound C-216, and the synthesis route of the aromatic amine compound is as follows:
  • Example 2 The method is the same as Example 1, except that B-216 (4.72 g, 10 mmol) replaces B-1, and the final product C-216 is obtained: 5.51 g (yield: 71%), MS (m/z) (M+): 776.
  • This embodiment provides an aromatic amine compound C-219, and the synthesis route of the aromatic amine compound is as follows:
  • This embodiment provides an aromatic amine compound C-221, and the synthesis route of the aromatic amine compound is as follows:
  • Example 2 The method is the same as Example 1, except that B-221 (4.72 g, 10 mmol) replaces B-1, and the final product C-221 is obtained: 6.44 g (yield: 83%), MS (m/z) (M+): 776.
  • This embodiment provides an aromatic amine compound C-227, and the synthesis route of the aromatic amine compound is as follows:
  • This embodiment provides an aromatic amine compound C-228, and the synthesis route of the aromatic amine compound is as follows:
  • Example 2 The method is the same as Example 1, except that B-228 (5.00 g, 10 mmol) replaces B-1, and the final product C-228 is 6.76 g (yield: 84%), MS (m/z) (M+): 805.
  • This embodiment provides an aromatic amine compound C-237, and the synthesis route of the aromatic amine compound is as follows:
  • This embodiment provides an aromatic amine compound C-255, and the synthesis route of the aromatic amine compound is as follows:
  • Example 2 The method is the same as Example 1, except that B-255 (4.96 g, 10 mmol) replaces B-1, and the final product C-255 is 6.56 g (yield: 82%), MS (m/z) (M+): 800.
  • This embodiment provides an aromatic amine compound C-278, and the synthesis route of the aromatic amine compound is as follows:
  • Example 2 The method is the same as Example 1, except that B-278 (3.71 g, 10 mmol) replaces B-1, and the final product C-278 is 5.21 g (yield: 77%), MS (m/z) (M+): 676.
  • This embodiment provides an aromatic amine compound C-283, and the synthesis route of the aromatic amine compound is as follows:
  • This embodiment provides an aromatic amine compound C-299, and the synthesis route of the aromatic amine compound is as follows:
  • Example 2 The method is the same as Example 1, except that B-299 (5.13 g, 10 mmol) replaces B-1, and the final product C-299 is 6.70 g (yield: 82%), MS (m/z) (M+): 817.
  • This comparative example provides a compound D1 that has been tested during the research process, and its specific structural formula is:
  • This comparative example provides a compound D2 that has been tested during the research process, and its specific structural formula is:
  • This comparative example provides a compound D3 that has been tested during the research process, and its specific structural formula is:
  • Gaussian 09W software was used based on the density functional theory (DFT) calculation method (the basis set level was set to: 6-311+G(2d,p), and the charge number was 0), and the molecular structures of C-1, C-2, C-3, C-4, C-11, C-20, C-29, C-52, C-53, C-73, C-111, C-121, C-131, C-172, C-180, C-186, C-227, C-228, C-237, C-299, D1, D2 and D3 were selected for geometric optimization.
  • Table 1 Table 1 below:
  • the aromatic amine compound provided by the present invention has a relatively large energy gap value, a relatively high LUMO value and a relatively large T1 compared with the comparative example compound.
  • the aromatic amine compound provided by the present invention is used as a hole transport layer material or a luminescent auxiliary layer material, and its energy level is more matched with the energy level of the adjacent organic layer, which can block electrons or excitons from leaving the luminescent layer; in addition, it can be seen from the data in Table 1 that the molecular weight of the aromatic amine compound provided by the present invention is mainly between 700 and 850, and the molecular weight of some compounds containing more condensed ring structures can reach more than 850.
  • the aromatic amine compound provided by the present invention has a relatively large molecular weight, and the molecular weight of the quaternary biphenyl in the parent core accounts for more than 35% of the molecular weight of the entire aromatic amine compound.
  • the aromatic amine compound has a relatively high glass transition temperature and thermal stability, avoiding the introduction of other unnecessary large molecular weight fragments in order to increase Tg in the later stage. Therefore, the aromatic amine compound provided by the present invention can meet the requirements of the organic electroluminescent device for the hole transport layer or the luminescent auxiliary layer.
  • the organic electroluminescent device of the following embodiment includes an anode 2, a hole transport region, a light-emitting layer 5, an electron transport region, and a cathode 8, which are sequentially arranged on a substrate 1; wherein the hole transport region includes a hole transport layer 3 and a light-emitting auxiliary layer 4; the electron transport region includes an electron transport layer 6 and an electron injection layer 7; the light-emitting layer 5 is composed of a host and a doped guest, and the host of the light-emitting layer can be composed of one molecular material or multiple molecular materials.
  • the typical structure of an organic electroluminescent device is shown in FIG1 .
  • the anode of the following embodiments adopts anode materials commonly used in the art, such as ITO, Ag or their multilayer structures.
  • the hole injection unit adopts hole injection materials commonly used in the art, and F4TCNQ, HATCN, NDP-9, etc. are added for doping.
  • the hole transport unit adopts hole transport materials commonly used in the art.
  • the light-emitting unit adopts light-emitting materials commonly used in the art, for example, it can be composed of a host material and an emitted guest material doped, and the emitted guest material can be an organic material such as a pyrene compound, or it can be a metal complex (such as metal Ir, Pt, etc.).
  • the electron transport unit adopts electron transport materials commonly used in the art.
  • the electron injection layer adopts electron injection materials commonly used in the art, such as Liq, LiF, Yb, etc.
  • the cathode adopts materials commonly used in the art, such as metal Al, Ag or metal mixtures (Ag-doped Mg, Ag-doped Ca, etc.).
  • each functional layer in the following embodiments is conventional methods in the art, such as vacuum thermal evaporation or inkjet printing, etc., which will not be described in detail here. Only some process details and test methods in the preparation process are supplemented as follows:
  • the present embodiment provides a red light organic electroluminescent device, and the preparation method thereof is as follows: first, on the ITO layer (anode) formed on the substrate, HTL and F4TCNQ (the mass ratio of HTL to F4TCNQ is 97:3) are vacuum deposited with a thickness of 10 nm to form a hole injection layer; secondly, on the hole injection layer, HTL is vacuum deposited with a thickness of 120 nm to form a hole transport layer; secondly, on the hole transport layer, C-1 is vacuum deposited with a thickness of 80 nm to form a light-emitting auxiliary layer; thirdly, on the light-emitting auxiliary layer, C-1 is vacuum deposited with a thickness of 40 nm to form a light-emitting auxiliary layer; The mixture of RH and RD forms a light-emitting layer, wherein RH is the main body and RD is the dopant, and the mass ratio of the main body to the dopant is 97:3; then
  • This embodiment provides a red light organic electroluminescent device, and its preparation method is as follows: the compound C-1 in the red light device embodiment 1 is replaced by compounds C-4, C-9, C-11, C-14, C-20, C-52, C-53, C-73 and C-84 to form a light-emitting auxiliary layer, and the other preparation steps are the same as those in the red light device embodiment 1, and red light organic electroluminescent devices are prepared respectively.
  • This comparative example provides a red light organic electroluminescent device that was experimented during the research process.
  • the preparation method thereof is as follows: Compound C1 in Example 1 of the red light device is replaced by comparative compound D1 to form a light-emitting auxiliary layer, and the other preparation steps are the same as those in Example 1 of the red light device to prepare a red light organic electroluminescent device.
  • the present embodiment provides a green light organic electroluminescent device, and the preparation method thereof is as follows: first, on the ITO layer (anode) formed on the substrate, HTL and F4TCNQ (the mass ratio of HTL to F4TCNQ is 97:3) are vacuum deposited with a thickness of 10 nm to form a hole injection layer; secondly, on the hole injection layer, HTL is vacuum deposited with a thickness of 120 nm to form a hole transport layer; secondly, on the hole transport layer, C-111 is vacuum deposited with a thickness of 30 nm to form a light-emitting auxiliary layer; thirdly, on the light-emitting auxiliary layer, GPH, GNH and GD are vacuum deposited with a thickness of 35 nm.
  • the mixture forms a light-emitting layer, wherein GPH and GNH are mixed evenly at a mass ratio of 4:6 as the main body, GD is used as the dopant, and the mass ratio of the main body to the dopant is 95:5; then on the above-mentioned light-emitting layer, a mixture of ET-01 and Liq is vacuum deposited at a thickness of 35nm to form an electron transport layer, wherein the mass ratio of ET-01 to Liq is 1:1; then on the above-mentioned electron transport layer, LiF is deposited at a thickness of 0.2nm to form an electron injection layer, and finally on the above-mentioned electron injection layer, aluminum (Al) is deposited at a thickness of 150nm to form a cathode, and a green light organic electroluminescent device is prepared. Except for the light-emitting auxiliary layer, the molecular structure formula of the remaining layers of materials is as follows:
  • This embodiment provides a green light organic electroluminescent device, and its preparation method is as follows: the compound C-111 in the green light device embodiment 1 is replaced by compounds C-115, C-121, C-131, C-133, C-164, C-172, C-180, C-181 and C-186 to form a luminescent auxiliary layer, and the other preparation steps are the same as those in the green light device embodiment 1, and green light organic electroluminescent devices are prepared respectively.
  • This comparative example provides a green organic electroluminescent device that has been experimented during the research process.
  • the preparation method thereof is as follows: the compound C-111 in the green light device example 1 is replaced with the comparative compound D2 to form a luminescent auxiliary layer, and the other preparation steps are the same as those in the green light device example 1 to prepare a green organic electroluminescent device.
  • the present embodiment provides a blue light organic electroluminescent device, and the preparation method thereof is as follows: first, on the ITO layer (anode) formed on the substrate, HTL and F4TCNQ (the mass ratio of HTL to F4TCNQ is 97:3) are vacuum deposited with a thickness of 10 nm to form a hole injection layer; secondly, on the hole injection layer, HTL is vacuum deposited with a thickness of 120 nm to form a hole transport layer; secondly, on the hole transport layer, C-216 is vacuum deposited with a thickness of 10 nm to form a light-emitting auxiliary layer; thirdly, on the light-emitting auxiliary layer, A mixture of BH and BD was vacuum deposited at a thickness of 20nm to form a light-emitting layer, wherein BH was used as a host and BD was used as a dopant, and the mass ratio of the host to the dopant was 98:2; then, a mixture of ET-01 and Liq
  • This embodiment provides a blue light organic electroluminescent device, and its preparation method is as follows: the compound C-216 in the blue light device embodiment 1 is replaced by compounds C-219, C-221, C-227, C-228, C-237, C-255, C-278, C-283 and C-299 to form a luminescent auxiliary layer, and the other preparation steps are the same as those in the blue light device embodiment 1, and blue light organic electroluminescent devices are prepared respectively.
  • This embodiment provides a blue light organic electroluminescent device, and its preparation method is as follows: the compound C-216 in the blue light device embodiment 1 is replaced by P-1 to form a light-emitting auxiliary layer, and the hole transport layer materials in the blue light device embodiment 1 are replaced by compounds C-2, C-3, C-16, C-17, C-21, C-22, C-23, C-26, C-29 and C-31 respectively, and the other preparation steps are the same as those in the blue light device embodiment 1, and blue light organic electroluminescent devices are prepared respectively.
  • This comparative example provides a blue light organic electroluminescent device that was experimented during the research process.
  • the preparation method thereof is: replacing the compound C-216 in the blue light device embodiment 1 with the comparative compound D3 to form a luminescent auxiliary layer, and the other preparation methods are the same as those in the blue light device embodiment 1 to prepare a blue light organic electroluminescent device.
  • This comparative example provides a blue light organic electroluminescent device that has been experimented during the research process.
  • the preparation method thereof is as follows: the compound C-216 in the blue light device embodiment 1 is replaced by P-1 to form a luminescent auxiliary layer, and the other preparation steps are the same as those in the blue light device embodiment 1 to prepare a blue light organic electroluminescent device.
  • IVL characteristic line current/voltage/luminous density characteristic line
  • the organic electroluminescent devices provided by the red light device embodiments 1-10, the red light device comparative example 1, the green light device embodiments 1-10, the green light device comparative example 1, the blue light device embodiments 1-20 and the blue light device comparative example 1-2 were subjected to performance tests.
  • the specific testing instruments and methods are as follows: the brightness was tested using a spectrum scanner PhotoResearch PR-635; the current density and the light-on voltage were tested using a digital source meter Keithley 2400; the life test was performed using an LT-96ch life test device; the specific test results are shown in Tables 2 to 5:
  • the driving voltage of the organic electroluminescent device prepared by using the aromatic amine compound provided by the present invention as the hole transport layer material or the luminescent auxiliary layer is significantly reduced, the luminescent efficiency is significantly improved, and the life is significantly prolonged. It is speculated that the reason is that the aromatic amine compound provided by the present invention contains a quaternary phenyl structure with a special connection mode, and the 3rd position and the 5th position of the benzene connected to nitrogen in the quaternary phenyl are replaced by monophenyl and diphenyl respectively.
  • This special connection mode makes the aromatic amine compound provided by the present invention have a relatively high LUMO and energy gap value.
  • the aromatic amine compound provided by the present invention is used as a hole transport layer material or a luminescent auxiliary layer material, the hole transport layer material or the luminescent auxiliary layer material is connected to the adjacent organic
  • the energy level of the layer is more matched, and it can block electrons or excitons from leaving the light-emitting layer, so it can effectively reduce the driving voltage of the organic electroluminescent device and improve the efficiency of the device;
  • this special connection method makes the aromatic amine compound provided by the present invention have an appropriate degree of conjugation, so it has a relatively high T1 value.
  • the aromatic amine compound provided by the present invention is used as a hole transport layer material or a light-emitting auxiliary layer material.
  • the energy transferred by the carriers of the hole transport layer or the light-emitting auxiliary layer can meet the light-emitting energy required for the transition of the light-emitting layer, so it can significantly improve the luminous efficiency of the organic electroluminescent device;
  • the molecular weight of the aromatic amine compound provided by the present invention is greater than 650, which can avoid the glass transition temperature being too low, inhibit the decomposition of the material, and then effectively improve the device life. This shows that the aromatic amine compound provided by the present invention is a hole transport layer material or a light-emitting auxiliary layer material with good performance, which can meet the performance requirements of organic electroluminescent devices and has practical value.

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Abstract

Disclosed are an aromatic amine compound comprising a quaterphenyl structure and an organic electroluminescent device comprising the same. The aromatic amine compound has a structure represented by formula (I). The compound has the following advantages by taking formula (I) as a mother nucleus: In one aspect, the mother nucleus has a relatively large molecular weight, which can effectively improve the glass transition temperature and thermal stability of the aromatic amine compound, and in another aspect, the special connection mode of the mother nucleus can reduce the steric hindrance and improve the LUMO, the energy gap value, and the T1 value of the aromatic amine compound. By applying the aromatic amine compound provided by the present invention to a hole transport layer material or a light-emitting auxiliary layer, the hole transport layer material or the light-emitting auxiliary layer material is more matched with the energy level of the adjacent organic layer, which can significantly improve the light-emitting efficiency of the organic electroluminescent device. The preparation process of the aromatic amine compound is simple and easy to implement, the starting materials are easy to obtain, and the aromatic amine compound is suitable for mass production and scale-up;

Description

一种包含四联苯结构的芳香胺化合物及包含其的有机电致发光器件Aromatic amine compound containing quaternary phenyl structure and organic electroluminescent device containing the same 技术领域Technical Field
本发明涉及有机发光半导体技术领域。更具体地，涉及一种包含四联苯结构的芳香胺化合物及包含其的有机电致发光器件。The present invention relates to the technical field of organic light-emitting semiconductors, and more specifically to an aromatic amine compound containing a quaternary phenyl structure and an organic electroluminescent device containing the same.
背景技术Background technique
有机电致发光器件通常由阴极、电子注入层、电子传输层、发光层、空穴传输层、空穴注入层和阳极构成，电子和空穴在外加电场下分别从阴极和阳极注入，然后相向运动，空穴经由空穴传输层传输到发光层，电子经由电子传输层传输到发光层中，在发光层中相遇的电子和空穴复合，形成电子-空穴对，即激子，然后激子辐射跃迁产生光发射。其中，由于空穴传输层材料的最高已占据分子轨道(HOMO)值较低，因此在发光层中生成的激子很容易扩散到空穴传输层界面或者空穴传输层侧，最终导致在发光层内界面的发光或者发光层内的电荷不均衡，从而在空穴传输层的界面上发光，使有机电致发光器件的色纯度及效率变低，最终导致有机电致发光器件的发光效率降低和使用寿命变短。提高空穴传输层材料的性能或者向发光层和空穴传输层之间引入发光辅助层，可以有效避免上述技术问题。发光辅助层具有辅助空穴传输层的作用，并且可以阻挡从阴极转移的电子，以将电子限制在发光层内，增加空穴的利用率，从而改善器件的发光效率和寿命。Organic electroluminescent devices are usually composed of a cathode, an electron injection layer, an electron transport layer, a light-emitting layer, a hole transport layer, a hole injection layer and an anode. Electrons and holes are injected from the cathode and anode respectively under an external electric field, and then move toward each other. Holes are transported to the light-emitting layer via the hole transport layer, and electrons are transported to the light-emitting layer via the electron transport layer. The electrons and holes that meet in the light-emitting layer recombine to form electron-hole pairs, i.e., excitons, and then the excitons radiate and transition to produce light emission. Among them, since the highest occupied molecular orbital (HOMO) value of the hole transport layer material is low, the excitons generated in the light-emitting layer can easily diffuse to the hole transport layer interface or the hole transport layer side, which ultimately leads to light emission at the interface of the light-emitting layer or charge imbalance in the light-emitting layer, thereby emitting light at the interface of the hole transport layer, reducing the color purity and efficiency of the organic electroluminescent device, and ultimately leading to reduced luminous efficiency and shortened service life of the organic electroluminescent device. Improving the performance of the hole transport layer material or introducing a light-emitting auxiliary layer between the light-emitting layer and the hole transport layer can effectively avoid the above technical problems. The light-emitting auxiliary layer has the function of assisting the hole transport layer and can block the electrons transferred from the cathode to confine the electrons in the light-emitting layer, increase the utilization rate of holes, and thus improve the luminous efficiency and life of the device.
但现有的空穴传输层材料以及发光辅助层材料普遍存在能级和能量搭配不好等问题，导致驱动电压较高。为了降低有机电致发光器件的驱动电压，目前常用的技术手段为在有机电致发光器件的空穴传输层材料或发光辅助层材料中引入萘、芴、菲等刚性平面共轭结构，这些结构具有较大的π电子云，有利于降低器件驱动电压，但此类结构会加深有机分子的共轭程度，导致空穴传输层材料或发光辅助层材料的T1显著下降，当发光辅助层载流子所传递的能量不能够满足发光层跃迁所需的发光能量时，有机电致发光器件的效率就会显著下降，并且此类结构在高温下或电激发态容易发生断键，从而降低有机电致发光器件的寿命。因此亟待开发一种新型的有机电致发光材料。However, existing hole transport layer materials and luminescent auxiliary layer materials generally have problems such as poor energy level and energy matching, resulting in a high driving voltage. In order to reduce the driving voltage of organic electroluminescent devices, the commonly used technical means are to introduce rigid planar conjugated structures such as naphthalene, fluorene, and phenanthrene into the hole transport layer materials or luminescent auxiliary layer materials of organic electroluminescent devices. These structures have a large π electron cloud, which is conducive to reducing the device driving voltage, but such structures will deepen the degree of conjugation of organic molecules, resulting in a significant decrease in the T1 of the hole transport layer material or the luminescent auxiliary layer material. When the energy transferred by the luminescent auxiliary layer carriers cannot meet the luminescent energy required for the transition of the luminescent layer, the efficiency of the organic electroluminescent device will be significantly reduced, and such structures are prone to bond breaking at high temperatures or in an electrically excited state, thereby reducing the life of the organic electroluminescent device. Therefore, it is urgent to develop a new type of organic electroluminescent material.
发明内容Summary of the invention
鉴于此，本发明提供一种包含四联苯结构的芳香胺化合物及包含其的有机电致发光器件，该芳香胺化合物不仅具有相对较高的HOMO、LUMO能级和较高的T1，还具有高的玻璃化转变温度和分子热稳定性，可用作有机电致发光器件的空穴传输层材料或发光辅助层材料，能够有效降低有机电致发光器件的驱动电压、提高器件的效率和延长器件的寿命，克服了现有技术的缺陷。In view of this, the present invention provides an aromatic amine compound containing a quaternary phenyl structure and an organic electroluminescent device containing the same. The aromatic amine compound not only has relatively high HOMO and LUMO energy levels and high T1, but also has high glass transition temperature and molecular thermal stability, and can be used as a hole transport layer material or a luminescent auxiliary layer material of an organic electroluminescent device, and can effectively reduce the driving voltage of the organic electroluminescent device, improve the efficiency of the device and extend the life of the device, thereby overcoming the defects of the prior art.
为达到上述发明目的，本发明采用了如下的技术方案：本发明第一方面提供了一种包含四联苯结构的芳香胺化合物，所述芳香胺化合物的结构式如式Ⅰ所示：
In order to achieve the above-mentioned object of the invention, the present invention adopts the following technical scheme: In the first aspect of the present invention, an aromatic amine compound containing a quaternary phenyl structure is provided, and the structural formula of the aromatic amine compound is shown in Formula I:
其中，所述Ar1、Ar2各自独立地选自取代或未取代的C6～C60的芳基、取代或未取代的C5～C60的杂芳基、取代或未取代的C10～C60的稠环芳基、取代或未取代的C9～C60的杂稠环芳基、取代或未取代的C3～C30的环烷基中的任意一种；Wherein, Ar 1 and Ar 2 are each independently selected from any one of a substituted or unsubstituted C 6 ～C 60 aryl group, a substituted or unsubstituted C 5 ～C 60 heteroaryl group, a substituted or unsubstituted C 10 ～C 60 condensed ring aryl group, a substituted or unsubstituted C 9 ～C 60 heterocondensed ring aryl group, and a substituted or unsubstituted C 3 ～C 30 cycloalkyl group;
当所述Ar1或Ar2存在取代基时，所述取代基选自氘、卤素、羟基、氰基、硝基、氨基、羧基或其盐、磺酸基或其盐、磷酸基或其盐、C1～C10的烷基、C6～C60的芳基、C5～C60的杂芳基、C10～C60的稠环芳基、C9～C60的杂稠环芳基或C3～C30的环烷基中的任意一种，其 中两个或两个以上的取代基可以相同或不同，可以彼此连接形成脂肪环、芳环、杂芳环、稠环或杂稠环；When Ar1 or Ar2 has a substituent, the substituent is selected from any one of deuterium, halogen, hydroxyl, cyano, nitro, amino, carboxyl or its salt, sulfonic acid or its salt , phosphate or its salt, C1-C10 alkyl, C6-C60 aryl, C5-C60 heteroaryl, C10 - C60 fused ring aryl , C9 - C60 heterofused ring aryl or C3 - C30 cycloalkyl, wherein The two or more substituents may be the same or different and may be connected to form an aliphatic ring, an aromatic ring, a heteroaromatic ring, a condensed ring or a heterocondensed ring;
所述L2选自单键、取代或未取代的C1～C12的亚烷基、取代或未取代的C6～C30的亚芳基、取代或未取代的C6～C30的亚杂芳基中的任意一种；The L2 is selected from any one of a single bond, a substituted or unsubstituted C1 - C12 alkylene group, a substituted or unsubstituted C6 - C30 arylene group, and a substituted or unsubstituted C6 - C30 heteroarylene group;
所述式I所示化合物上的任意一个氢可以各自独立地被氘、烷基或环烷基取代。Any hydrogen on the compound of formula I can be independently replaced by deuterium, alkyl or cycloalkyl.
结合第一方面，所述Ar1的结构式如式Ⅱ所示：
In combination with the first aspect, the structural formula of Ar 1 is shown in Formula II:
其中，所述R1、R2各自独立地选自氢、氘、取代或未取代的C1～C10的烷基、取代或未取代的C3～C10的环烷基、取代或未取代的C6～C30的芳基、取代或未取代的C5～C30的杂芳基、取代或未取代的C1～C6的烷氧基、取代或未取代的C10～C60的稠环基、取代或未取代的C9～C30的芳烷基、取代或未取代的C6～C30的芳氧基、取代或未取代的C6～C30芳胺基中的任意一种，上述任意两个或两个以上的基团可以彼此连接形成脂肪环、芳环、杂芳环、稠环或杂稠环；Wherein, R 1 and R 2 are each independently selected from any one of hydrogen, deuterium, substituted or unsubstituted C 1 to C 10 alkyl, substituted or unsubstituted C 3 to C 10 cycloalkyl, substituted or unsubstituted C 6 to C 30 aryl, substituted or unsubstituted C 5 to C 30 heteroaryl, substituted or unsubstituted C 1 to C 6 alkoxy, substituted or unsubstituted C 10 to C 60 condensed ring, substituted or unsubstituted C 9 to C 30 aralkyl, substituted or unsubstituted C 6 to C 30 aryloxy, substituted or unsubstituted C 6 to C 30 arylamine, and any two or more of the above groups can be connected to form an aliphatic ring, an aromatic ring, a heteroaromatic ring, a condensed ring or a heterocondensed ring;
所述a选自1至5的整数；所述b选自1至4的整数；The a is selected from an integer from 1 to 5; the b is selected from an integer from 1 to 4;
所述L1选自单键、O、S、取代或未取代的C1～C12的亚烷基、取代或未取代的C6～C30的亚芳基中的任意一种；The L1 is selected from any one of a single bond, O, S, a substituted or unsubstituted C1 - C12 alkylene group, and a substituted or unsubstituted C6 - C30 arylene group;
所述式Ⅱ所示化合物上的任意一个氢可以各自独立地被氘、烷基或环烷基取代。Any hydrogen on the compound represented by formula II can be independently replaced by deuterium, alkyl or cycloalkyl.
结合第一方面，所述式Ⅱ所示的化合物为下述式Ⅱ-1～式Ⅱ-7所示结构中的一种：
In combination with the first aspect, the compound represented by formula II is one of the structures represented by the following formula II-1 to formula II-7:
其中，所述n选自1至4的整数；所述m选自1至3的整数；Wherein, n is selected from an integer from 1 to 4; m is selected from an integer from 1 to 3;
所述L1选自单键、O、S、取代或未取代的C1～C12的亚烷基、取代或未取代的C6～C30的亚芳基中的任意一种；The L1 is selected from any one of a single bond, O, S, a substituted or unsubstituted C1 - C12 alkylene group, and a substituted or unsubstituted C6 - C30 arylene group;
所述L2选自单键、O、S中的任意一种；The L2 is selected from any one of a single bond, O, and S;
所述X选自O、S、CR3R4、NR5中的任意一种；The X is selected from any one of O, S, CR 3 R 4 and NR 5 ;
所述R3、R4各自独立地选自氢、氘、取代或未取代的C1～C10的烷基、取代或未取代 的C6～C30的芳基、取代或未取代的C5～C30的杂芳基、取代或未取代的C10～C60的稠环基、取代或未取代的C6～C30的芳烷基、取代或未取代的C6～C30的芳氧基、取代或未取代的C6～C30芳硫基，R3、R4可以彼此连接形成脂肪环、芳环、杂芳环、稠环或杂稠环；The R 3 and R 4 are each independently selected from hydrogen, deuterium, substituted or unsubstituted C 1 to C 10 alkyl, substituted or unsubstituted substituted or unsubstituted C 6 ～C 30 aryl group, substituted or unsubstituted C 5 ～C 30 heteroaryl group, substituted or unsubstituted C 10 ～C 60 condensed ring group, substituted or unsubstituted C 6 ～C 30 aralkyl group, substituted or unsubstituted C 6 ～C 30 aryloxy group, substituted or unsubstituted C 6 ～C 30 arylthio group, R 3 and R 4 can be connected to each other to form an aliphatic ring, an aromatic ring, a heteroaromatic ring, a condensed ring or a heterocondensed ring;
所述R5选自氢、氘、取代或未取代的C1～C10的烷基、取代或未取代的C6～C30的芳基；The R 5 is selected from hydrogen, deuterium, substituted or unsubstituted C 1 to C 10 alkyl, substituted or unsubstituted C 6 to C 30 aryl;
所述式Ⅱ-1～式Ⅱ-7所示化合物上的任意一个氢可以各自独立地被氘、烷基或环烷基取代。Any hydrogen on the compounds represented by formula II-1 to formula II-7 can be independently replaced by deuterium, alkyl or cycloalkyl.
结合第一方面，所述Ar2选自取代或未取代的C6～C30的芳基、取代或未取代的C5～C30的杂芳基、取代或未取代的C10～C30的稠环芳基、取代或未取代的C9～C30的杂稠环芳基、取代或未取代的C3～C15的环烷基中的任意一种。In combination with the first aspect, Ar2 is selected from any one of a substituted or unsubstituted C6 - C30 aryl group, a substituted or unsubstituted C5 - C30 heteroaryl group, a substituted or unsubstituted C10 - C30 condensed ring aryl group, a substituted or unsubstituted C9 - C30 heterocondensed ring aryl group, and a substituted or unsubstituted C3 - C15 cycloalkyl group.
结合第一方面，所述Ar2选自下列a-1至a-92所示基团中的任意一种：



In combination with the first aspect, Ar 2 is selected from any one of the following groups represented by a-1 to a-92:



结合第一方面，所述L2选自单键、中的任意一种。In combination with the first aspect, the L2 is selected from a single bond, Any one of .
可以理解，上述例举的当L2选自单键、中的任意一种时，表示这些基团中，苯环上的任意能够成键的位置均可作为连接位点。It is understood that when L2 is selected from a single bond, When any of the above is used, it means that in these groups, any bonding position on the benzene ring can serve as a bonding site.
结合第一方面，所述式Ⅰ所示化合物选自下述所示化合物中的任意一种：
































In combination with the first aspect, the compound represented by formula I is selected from any one of the following compounds:
































本发明第二方面提供了上述芳香胺化合物在有机电致发光器件中的应用。The second aspect of the present invention provides use of the aromatic amine compound in an organic electroluminescent device.
本发明第三方面提供了一种有机电致发光器件，包括依次设置在衬底基板上的阳极、空穴传输层、发光辅助层、发光层、电子传输区和阴极；其中，所述发光辅助层和/或空穴传输层中包括一种或多种如上所述的芳香胺化合物。The third aspect of the present invention provides an organic electroluminescent device, comprising an anode, a hole transport layer, a luminescence auxiliary layer, a luminescent layer, an electron transport region and a cathode arranged in sequence on a substrate; wherein the luminescence auxiliary layer and/or the hole transport layer comprises one or more aromatic amine compounds as described above.
本发明的有益效果如下：The beneficial effects of the present invention are as follows:
本发明提供的芳香胺化合物以式i为母核具有如下优势，一方面，该母核具有相对较大的分子量，能够有效提高芳香胺化合物的玻璃化转变温度和热稳定性，另一方面，与氮连接的苯的3号位置与5号位置分别被二联苯和单苯取代，与3号位置连接的二联苯为邻位取代，以该特殊的方式连接能够降低空间位阻，并且提高芳香胺化合物的LUMO、能隙值以及T1值；将本发明提供的芳香胺化合物应用于有机电致发光器件的空穴传输层材料或发光辅助层中，该空穴传输层材料或发光辅助层材料的能级与邻近有机层的能级更加匹配，能够有效降低有机电致发光器件的驱动电压；该空穴传输层材料或发光辅助层材料具有相对较高的LUMO和能隙值，能够阻挡电子或激子离开发光层，从而提高器件的效率；该空穴传输层材料或发光辅助层材料具有相对较高的T1值，该空穴传输层或发光辅助层的载流子所传递的能量能够满足发光层跃迁所需的发光能量，因此能够显著提高有机电致发光器件的发光效率；该空穴传输层材料或发光辅助层材料具有较高的玻璃化转变温度和热稳定性，能够抑制材料的蒸镀分解，有效提高器件寿命；克服了现有技术的缺陷。The aromatic amine compound provided by the present invention has the following advantages with Formula I as the parent core: on the one hand, the parent core has a relatively large molecular weight, which can effectively improve the glass transition temperature and thermal stability of the aromatic amine compound; on the other hand, the 3rd position and the 5th position of the benzene connected to nitrogen are substituted by biphenyl and monophenyl respectively, and the biphenyl connected to the 3rd position is ortho-substituted. The connection in this special way can reduce the steric hindrance and improve the LUMO, energy gap value and T1 value of the aromatic amine compound; the aromatic amine compound provided by the present invention is applied to the hole transport layer material or the light-emitting auxiliary layer of the organic electroluminescent device, and the energy level of the hole transport layer material or the light-emitting auxiliary layer material is more matched with the energy level of the adjacent organic layer. The invention discloses a method for preparing an organic electroluminescent device having a hole transport layer material or a light-emitting auxiliary layer material, which can effectively reduce the driving voltage of the organic electroluminescent device; the hole transport layer material or the light-emitting auxiliary layer material has a relatively high LUMO and energy gap value, which can block electrons or excitons from leaving the light-emitting layer, thereby improving the efficiency of the device; the hole transport layer material or the light-emitting auxiliary layer material has a relatively high T1 value, and the energy transferred by the carriers of the hole transport layer or the light-emitting auxiliary layer can meet the light-emitting energy required for the transition of the light-emitting layer, thereby significantly improving the light-emitting efficiency of the organic electroluminescent device; the hole transport layer material or the light-emitting auxiliary layer material has a high glass transition temperature and thermal stability, which can inhibit the evaporation and decomposition of the material and effectively improve the life of the device; and overcomes the defects of the prior art.
本发明化合物的制备工艺简单易行，原料易得，适合于量产放大。
The preparation process of the compound of the present invention is simple and easy, the raw materials are easily available, and it is suitable for mass production and expansion.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
下面结合附图对本发明的具体实施方式作进一步详细的说明。The specific implementation modes of the present invention will be further described in detail below in conjunction with the accompanying drawings.
图1示出含有本发明的芳香胺化合物的有机电致发光器件的结构示意图；FIG1 is a schematic structural diagram of an organic electroluminescent device containing an aromatic amine compound of the present invention;
图2示出芳香胺化合物C1的LOMO分布图；FIG2 shows the LOMO distribution diagram of the aromatic amine compound C1;
图3示出芳香胺化合物C1的三线态能级轨道分布图；FIG3 shows a triplet energy level orbital distribution diagram of the aromatic amine compound C1;
图4示出芳香胺化合物C2的LOMO分布图；FIG4 shows the LOMO distribution diagram of the aromatic amine compound C2;
图5示出芳香胺化合物C2的三线态能级轨道分布图；FIG5 shows a triplet energy level orbital distribution diagram of the aromatic amine compound C2;
图6示出芳香胺化合物C3的LOMO分布图；FIG6 shows the LOMO distribution diagram of the aromatic amine compound C3;
图7示出芳香胺化合物C3的三线态能级轨道分布图；FIG7 shows a triplet energy level orbital distribution diagram of the aromatic amine compound C3;
图8示出芳香胺化合物C4的LOMO分布图；FIG8 shows the LOMO distribution diagram of the aromatic amine compound C4;
图9示出芳香胺化合物C4的三线态能级轨道分布图；FIG9 shows a triplet energy level orbital distribution diagram of aromatic amine compound C4;
图10示出芳香胺化合物C29的LOMO分布图；FIG10 shows the LOMO distribution diagram of aromatic amine compound C29;
图11示出芳香胺化合物C29的三线态能级轨道分布图；FIG11 shows a triplet energy level orbital distribution diagram of aromatic amine compound C29;
图12示出芳香胺化合物C180的LOMO分布图；FIG12 shows the LOMO distribution diagram of aromatic amine compound C180;
图13示出芳香胺化合物C180的三线态能级轨道分布图；FIG13 shows a triplet energy level orbital distribution diagram of aromatic amine compound C180;
图14示出芳香胺化合物C216的LOMO分布图；FIG14 shows the LOMO distribution diagram of aromatic amine compound C216;
图15示出芳香胺化合物C216的三线态能级轨道分布图；FIG15 shows a triplet energy level orbital distribution diagram of aromatic amine compound C216;
图16示出芳香胺化合物C227的LOMO分布图；FIG16 shows the LOMO distribution diagram of aromatic amine compound C227;
图17示出芳香胺化合物C227的三线态能级轨道分布图。FIG17 shows the triplet energy level orbital distribution diagram of the aromatic amine compound C227.
附图说明：1-基板、2-阳极、3-空穴传输层、4-发光辅助层、5-发光层、6-电子传输层、7-电子注入层、8-阴极。Description of the drawings: 1-substrate, 2-anode, 3-hole transport layer, 4-luminescence auxiliary layer, 5-luminescent layer, 6-electron transport layer, 7-electron injection layer, 8-cathode.
具体实施方式Detailed ways
为了更清楚地说明本发明，下面结合优选实施例和附图对本发明做进一步的说明。附图中相似的部件以相同的附图标记进行表示。本领域技术人员应当理解，下面所具体描述的内容是说明性的而非限制性的，不应以此限制本发明的保护范围。本说明书的实施例和对比例是为了向本领域技术人员更完整的说明本说明书而提供的，根据本说明书的实施例和对比例可以变形为各种不同形态，本发明的保护范围不应仅限定于以下详述的实施例和对比例。In order to more clearly illustrate the present invention, the present invention is further described below in conjunction with preferred embodiments and accompanying drawings. Similar components in the accompanying drawings are represented by the same figure numerals. It should be understood by those skilled in the art that the content specifically described below is illustrative and not restrictive, and the protection scope of the present invention should not be limited to this. The embodiments and comparative examples of this specification are provided to more completely explain this specification to those skilled in the art. According to the embodiments and comparative examples of this specification, various different forms can be deformed, and the protection scope of the present invention should not be limited only to the embodiments and comparative examples described in detail below.
本发明的化合物适用于发光元件、显示面板及电子器件中，尤其适用于有机电致发光器件中。本发明的电子器件是包含至少一种有机化合物的层的器件，该器件也可以包含无机材料或完全由无机材料形成的层。电子器件优选有机电致发光器件(OLED)、有机集成电路(O-IC)、有机场效应晶体管(O-FET)、有机薄膜晶体管(O-TFT)、有机发光晶体管(O-LET)、有机太阳能电池(O-SC)、有机染料敏化的太阳能电池(O-DSSC)、有机光学检测器、有机光感受器、有机场猝熄器件(O-FQD)、发光电化学电池(LEC)、有机激光二极管(O-laser)和有机等离子体发射器件。电子器件优选有机电致发光器件(OLED)。示例性的有机电致发光器件的结构示意图如图1所示。The compounds of the present invention are suitable for use in light-emitting elements, display panels and electronic devices, and are particularly suitable for use in organic electroluminescent devices. The electronic device of the present invention is a device comprising a layer of at least one organic compound, which may also comprise an inorganic material or a layer formed entirely of an inorganic material. The electronic device is preferably an organic electroluminescent device (OLED), an organic integrated circuit (O-IC), an organic field effect transistor (O-FET), an organic thin film transistor (O-TFT), an organic light-emitting transistor (O-LET), an organic solar cell (O-SC), an organic dye-sensitized solar cell (O-DSSC), an organic optical detector, an organic photoreceptor, an organic field quenching device (O-FQD), a light-emitting electrochemical cell (LEC), an organic laser diode (O-laser) and an organic plasma emission device. The electronic device is preferably an organic electroluminescent device (OLED). The structural schematic diagram of an exemplary organic electroluminescent device is shown in Figure 1.
本发明的芳香胺化合物是利用作为代表性的反应布赫瓦尔德-哈特维希偶联反应、铃木偶联反应或Heck偶联反应制备得到。The aromatic amine compound of the present invention is prepared by using a representative reaction such as a Buchwald-Hartwig coupling reaction, a Suzuki coupling reaction or a Heck coupling reaction.
实施例1Example 1
本实施例提供一种中间体化合物A，该化合物的合成路线如下：
This embodiment provides an intermediate compound A, and the synthesis route of the compound is as follows:
在氮气保护下，将E(21.78g,0.11mol),F(31.20g,0.1mol)和碳酸钠(21.20g，0.2mol)加入300ml甲苯、乙醇和水的混合溶剂，混合溶剂中甲苯、水与乙醇的体积比为8：3：1，引入PdCl(PPh3)2(1.40g，2mmol)，随后将反应体系加热至80℃，回流并维持5小时，降至室温后加入200ml去离子水搅拌20min后分液，有机相过滤后使用无水硫酸钠干燥，旋除溶剂，粗产物通过柱色谱提纯。最终得到产物A:23.10g(收率：60％),MS(m/z)(M+):385。Under nitrogen protection, E (21.78g, 0.11mol), F (31.20g, 0.1mol) and sodium carbonate (21.20g, 0.2mol) were added to 300ml of a mixed solvent of toluene, ethanol and water, wherein the volume ratio of toluene, water and ethanol in the mixed solvent was 8:3:1, and PdCl(PPh 3 ) 2 (1.40g, 2mmol) was introduced, and then the reaction system was heated to 80°C, refluxed and maintained for 5 hours, cooled to room temperature, added with 200ml of deionized water, stirred for 20min and separated, the organic phase was filtered and dried over anhydrous sodium sulfate, the solvent was removed by rotation, and the crude product was purified by column chromatography. Finally, product A: 23.10g (yield: 60%), MS (m/z) (M+): 385 was obtained.
以下实施例中使用的中间体化合物A均由以上方式制备得到。The intermediate compound A used in the following examples was prepared in the above manner.
实施例2Example 2
本实施例提供一种芳香胺化合物C-1，该芳香胺化合物的合成路线如下：
This embodiment provides an aromatic amine compound C-1, and the synthesis route of the aromatic amine compound is as follows:
将A(3.85g，10mmol)，B-1(4.38g，10mmol)和叔丁醇钠(1.06g，11mmol)加入甲苯(50mL)中，然后在氮气保护下，引入双二亚苄基丙酮钯(0.09g，0.1mmol)和三叔丁基磷(0.08g，0.2mmol),随后将反应体系加热至110℃，回流并维持8小时，降至室温后加水淬灭并分液，有机相过滤后使用无水硫酸钠干燥，旋除溶剂，粗产物通过柱色谱提纯。最终得到产物C-1:5.42g(收率：73％),MS(m/z)(M+):742。A (3.85 g, 10 mmol), B-1 (4.38 g, 10 mmol) and sodium tert-butoxide (1.06 g, 11 mmol) were added to toluene (50 mL), and then bis(dibenzylideneacetonepalladium) (0.09 g, 0.1 mmol) and tri-tert-butylphosphine (0.08 g, 0.2 mmol) were introduced under nitrogen protection, and then the reaction system was heated to 110 ° C, refluxed and maintained for 8 hours, cooled to room temperature, quenched with water and separated, the organic phase was filtered and dried over anhydrous sodium sulfate, the solvent was removed by rotation, and the crude product was purified by column chromatography. Finally, the product C-1: 5.42 g (yield: 73%), MS (m/z) (M+): 742.
实施例3Example 3
本实施例提供一种芳香胺化合物C-2，该芳香胺化合物的合成路线如下：
This embodiment provides an aromatic amine compound C-2, and the synthesis route of the aromatic amine compound is as follows:
方法同实施例1，区别在于，将B-2(4.58g，10mmol)替换B-1，最终得到产物C-2:6.40g(收率：84％),MS(m/z)(M+):762。The method is the same as Example 1, except that B-2 (4.58 g, 10 mmol) replaces B-1, and finally the product C-2 is obtained: 6.40 g (yield: 84%), MS (m/z) (M+): 762.
实施例4Example 4
本实施例提供一种芳香胺化合物C-3，该芳香胺化合物的合成路线如下：
This embodiment provides an aromatic amine compound C-3, and the synthesis route of the aromatic amine compound is as follows:
方法同实施例1，区别在于，将B-3(4.58g，10mmol)替换B-1，最终得到产物C-3:6.02g(收率：79％),MS(m/z)(M+):762。The method is the same as Example 1, except that B-3 (4.58 g, 10 mmol) replaces B-1, and finally the product C-3 is obtained: 6.02 g (yield: 79%), MS (m/z) (M+): 762.
实施例5Example 5
本实施例提供一种芳香胺化合物C-4，该芳香胺化合物的合成路线如下：
This embodiment provides an aromatic amine compound C-4, and the synthesis route of the aromatic amine compound is as follows:
方法同实施例1，区别在于，将B-4(4.24g，10mmol)替换B-1，最终得到产物C-4:5.97g(收率：82％),MS(m/z)(M+):728。The method is the same as Example 1, except that B-4 (4.24 g, 10 mmol) replaces B-1, and finally the product C-4 is obtained: 5.97 g (yield: 82%), MS (m/z) (M+): 728.
实施例6Example 6
本实施例提供一种芳香胺化合物C-9，该芳香胺化合物的合成路线如下：
This embodiment provides an aromatic amine compound C-9, and the synthesis route of the aromatic amine compound is as follows:
方法同实施例1，区别在于，将B-9(4.79g，10mmol)替换B-1，最终得到产物C-9:6.03g(收率：77％),MS(m/z)(M+):783。The method is the same as Example 1, except that B-9 (4.79 g, 10 mmol) replaces B-1, and the final product C-9 is 6.03 g (yield: 77%), MS (m/z) (M+): 783.
实施例7Example 7
本实施例提供一种芳香胺化合物C-11，该芳香胺化合物的合成路线如下：
This embodiment provides an aromatic amine compound C-11, and the synthesis route of the aromatic amine compound is as follows:
方法同实施例1，区别在于，将B-11(4.51g，10mmol)替换B-1，最终得到产物C-11:5.59g(收率：74％),MS(m/z)(M+):755。The method is the same as Example 1, except that B-11 (4.51 g, 10 mmol) replaces B-1, and the final product C-11 is 5.59 g (yield: 74%), MS (m/z) (M+): 755.
实施例8Example 8
本实施例提供一种芳香胺化合物C-14，该芳香胺化合物的合成路线如下：
This embodiment provides an aromatic amine compound C-14, and the synthesis route of the aromatic amine compound is as follows:
方法同实施例1，区别在于，将B-14(4.69g，10mmol)替换B-1，最终得到产物C-14:6.18g(收率：80％),MS(m/z)(M+):773。The method is the same as Example 1, except that B-14 (4.69 g, 10 mmol) replaces B-1, and the final product C-14 is 6.18 g (yield: 80%), MS (m/z) (M+): 773.
实施例9Example 9
本实施例提供一种芳香胺化合物C-16，该芳香胺化合物的合成路线如下：
This embodiment provides an aromatic amine compound C-16, and the synthesis route of the aromatic amine compound is as follows:
方法同实施例1，区别在于，将A-16(4.02g，10mmol)替换A，将B-16(5.26g，10mmol)替换B-1，最终得到产物C-16:6.01g(收率：71％),MS(m/z)(M+):847。The method is the same as Example 1, except that A-16 (4.02 g, 10 mmol) replaces A, and B-16 (5.26 g, 10 mmol) replaces B-1, and finally the product C-16 is obtained: 6.01 g (yield: 71%), MS (m/z) (M+): 847.
实施例10Example 10
本实施例提供一种芳香胺化合物C-17，该芳香胺化合物的合成路线如下：
This embodiment provides an aromatic amine compound C-17, and the synthesis route of the aromatic amine compound is as follows:
方法同实施例1，区别在于，将B-17(5.75g，10mmol)替换B-1，最终得到产物C-17:6.68g(收率：76％),MS(m/z)(M+):879。The method is the same as Example 1, except that B-17 (5.75 g, 10 mmol) replaces B-1, and the final product C-17 is 6.68 g (yield: 76%), MS (m/z) (M+): 879.
实施例11Embodiment 11
本实施例提供一种芳香胺化合物C-20，该芳香胺化合物的合成路线如下：
This embodiment provides an aromatic amine compound C-20, and the synthesis route of the aromatic amine compound is as follows:
方法同实施例1，区别在于，将B-20(4.96g，10mmol)替换B-1，最终得到产物C-20:5.76g(收率：72％),MS(m/z)(M+):800。The method is the same as Example 1, except that B-20 (4.96 g, 10 mmol) replaces B-1, and finally the product C-20 is obtained: 5.76 g (yield: 72%), MS (m/z) (M+): 800.
实施例12Example 12
本实施例提供一种芳香胺化合物C-21，该芳香胺化合物的合成路线如下：
This embodiment provides an aromatic amine compound C-21, and the synthesis route of the aromatic amine compound is as follows:
方法同实施例1，区别在于，将B-21(5.24g，10mmol)替换B-1，最终得到产物C-21:5.80g(收率：70％),MS(m/z)(M+):828。The method is the same as Example 1, except that B-21 (5.24 g, 10 mmol) replaces B-1, and finally the product C-21 is obtained: 5.80 g (yield: 70%), MS (m/z) (M+): 828.
实施例13Example 13
本实施例提供一种芳香胺化合物C-22，该芳香胺化合物的合成路线如下：
This embodiment provides an aromatic amine compound C-22, and the synthesis route of the aromatic amine compound is as follows:
方法同实施例1，区别在于，将B-22(5.73g，10mmol)替换B-1，最终得到产物C-22:6.14g(收率：70％),MS(m/z)(M+):877。The method is the same as Example 1, except that B-22 (5.73 g, 10 mmol) replaces B-1, and finally the product C-22 is obtained: 6.14 g (yield: 70%), MS (m/z) (M+): 877.
实施例14Embodiment 14
本实施例提供一种芳香胺化合物C-23，该芳香胺化合物的合成路线如下：
This embodiment provides an aromatic amine compound C-23, and the synthesis route of the aromatic amine compound is as follows:
方法同实施例1，区别在于，将B-23(5.73g，10mmol)替换B-1，最终得到产物C-23:7.19g(收率：82％),MS(m/z)(M+):877。The method is the same as Example 1, except that B-23 (5.73 g, 10 mmol) replaces B-1, and finally the product C-23 is obtained: 7.19 g (yield: 82%), MS (m/z) (M+): 877.
实施例15Embodiment 15
本实施例提供一种芳香胺化合物C-26，该芳香胺化合物的合成路线如下：
This embodiment provides an aromatic amine compound C-26, and the synthesis route of the aromatic amine compound is as follows:
方法同实施例1，区别在于，将B-26(4.51g，10mmol)替换B-1，最终得到产物C-26:5.89g(收率：78％),MS(m/z)(M+):755。The method is the same as Example 1, except that B-26 (4.51 g, 10 mmol) replaces B-1, and finally the product C-26 is obtained: 5.89 g (yield: 78%), MS (m/z) (M+): 755.
实施例16Example 16
本实施例提供一种芳香胺化合物C-29，该芳香胺化合物的合成路线如下：
This embodiment provides an aromatic amine compound C-29, and the synthesis route of the aromatic amine compound is as follows:
方法同实施例1，区别在于，将B-29(4.69g，10mmol)替换B-1，最终得到产物C-29:6.34g(收率：82％),MS(m/z)(M+):773。The method is the same as Example 1, except that B-29 (4.69 g, 10 mmol) replaces B-1, and finally the product C-29 is obtained: 6.34 g (yield: 82%), MS (m/z) (M+): 773.
实施例17Embodiment 17
本实施例提供一种芳香胺化合物C-31，该芳香胺化合物的合成路线如下：
This embodiment provides an aromatic amine compound C-31, and the synthesis route of the aromatic amine compound is as follows:
方法同实施例1，区别在于，将B-31(5.40g，10mmol)替换B-1，最终得到产物C-31:6.75g(收率：80％),MS(m/z)(M+):844。The method is the same as Example 1, except that B-31 (5.40 g, 10 mmol) replaces B-1, and the final product C-31 is 6.75 g (yield: 80%), MS (m/z) (M+): 844.
实施例18Embodiment 18
本实施例提供一种芳香胺化合物C-52，该芳香胺化合物的合成路线如下：
This embodiment provides an aromatic amine compound C-52, and the synthesis route of the aromatic amine compound is as follows:
方法同实施例1，区别在于，将B-52(5.26g，10mmol)替换B-1，最终得到产物C-52:6.14g(收率：74％),MS(m/z)(M+):830。The method is the same as Example 1, except that B-52 (5.26 g, 10 mmol) replaces B-1, and the final product C-52 is obtained: 6.14 g (yield: 74%), MS (m/z) (M+): 830.
实施例19Embodiment 19
本实施例提供一种芳香胺化合物C-53，该芳香胺化合物的合成路线如下：
This embodiment provides an aromatic amine compound C-53, and the synthesis route of the aromatic amine compound is as follows:
方法同实施例1，区别在于，将B-53(5.33g，10mmol)替换B-1，最终得到产物C-53:6.53g(收率：78％),MS(m/z)(M+):837。The method is the same as Example 1, except that B-53 (5.33 g, 10 mmol) replaces B-1, and the final product C-53 is 6.53 g (yield: 78%), MS (m/z) (M+): 837.
实施例20Embodiment 20
本实施例提供一种芳香胺化合物C-73，该芳香胺化合物的合成路线如下：
This embodiment provides an aromatic amine compound C-73, and the synthesis route of the aromatic amine compound is as follows:
方法同实施例1，区别在于，将B-73(4.95g，10mmol)替换B-1，最终得到产物C-73:6.07g(收率：76％),MS(m/z)(M+):799。The method is the same as Example 1, except that B-73 (4.95 g, 10 mmol) replaces B-1, and the final product C-73 is obtained: 6.07 g (yield: 76%), MS (m/z) (M+): 799.
实施例21Embodiment 21
本实施例提供一种芳香胺化合物C-84，该芳香胺化合物的合成路线如下：
This embodiment provides an aromatic amine compound C-84, and the synthesis route of the aromatic amine compound is as follows:
方法同实施例1，区别在于，将B-84(5.76g，10mmol)替换B-1，最终得到产物C-84:7.13g(收率：81％),MS(m/z)(M+):880。The method is the same as Example 1, except that B-84 (5.76 g, 10 mmol) replaces B-1, and the final product C-84 is 7.13 g (yield: 81%), MS (m/z) (M+): 880.
实施例22Embodiment 22
本实施例提供一种芳香胺化合物C-111，该芳香胺化合物的合成路线如下：
This embodiment provides an aromatic amine compound C-111, and the synthesis route of the aromatic amine compound is as follows:
方法同实施例1，区别在于，将B-111(3.61g,10mmol)替换B-1，最终得到产物C-111:5.59g(收率：84％),MS(m/z)(M+):666。The method is the same as Example 1, except that B-111 (3.61 g, 10 mmol) replaces B-1, and finally the product C-111 is obtained: 5.59 g (yield: 84%), MS (m/z) (M+): 666.
实施例23Embodiment 23
本实施例提供一种芳香胺化合物C-115，该芳香胺化合物的合成路线如下：
This embodiment provides an aromatic amine compound C-115, and the synthesis route of the aromatic amine compound is as follows:
方法同实施例1，区别在于，将B-115(3.75g，10mmol)替换B-1，最终得到产物C-115:5.44g(收率：80％),MS(m/z)(M+):680。The method is the same as Example 1, except that B-115 (3.75 g, 10 mmol) replaces B-1, and finally the product C-115 is obtained: 5.44 g (yield: 80%), MS (m/z) (M+): 680.
实施例24Embodiment 24
本实施例提供一种芳香胺化合物C-121，该芳香胺化合物的合成路线如下：
This embodiment provides an aromatic amine compound C-121, and the synthesis route of the aromatic amine compound is as follows:
方法同实施例1，区别在于，将B-121(3.71g，10mmol)替换B-1，最终得到产物C-121:5.67g(收率：84％),MS(m/z)(M+):675。The method is the same as Example 1, except that B-121 (3.71 g, 10 mmol) replaces B-1, and the final product C-121 is 5.67 g (yield: 84%), MS (m/z) (M+): 675.
实施例25Embodiment 25
本实施例提供一种芳香胺化合物C-131，该芳香胺化合物的合成路线如下：
This embodiment provides an aromatic amine compound C-131, and the synthesis route of the aromatic amine compound is as follows:
方法同实施例1，区别在于，将B-131(4.93g，10mmol)替换B-1，最终得到产物C-131:5.66g(收率：71％),MS(m/z)(M+):797。The method is the same as Example 1, except that B-131 (4.93 g, 10 mmol) replaces B-1, and finally the product C-131 is obtained: 5.66 g (yield: 71%), MS (m/z) (M+): 797.
实施例26Embodiment 26
本实施例提供一种芳香胺化合物C-133，该芳香胺化合物的合成路线如下：
This embodiment provides an aromatic amine compound C-133, and the synthesis route of the aromatic amine compound is as follows:
方法同实施例1，区别在于，将B-133(4.84g，10mmol)替换B-1，最终得到产物C-133:6.70g(收率：85％),MS(m/z)(M+):788。The method is the same as Example 1, except that B-133 (4.84 g, 10 mmol) is used to replace B-1, and the final product C-133 is 6.70 g (yield: 85%), MS (m/z) (M+): 788.
实施例27Embodiment 27
本实施例提供一种芳香胺化合物C-164，该芳香胺化合物的合成路线如下：
This embodiment provides an aromatic amine compound C-164, and the synthesis route of the aromatic amine compound is as follows:
方法同实施例1，区别在于，将B-164(4.63g，10mmol)替换B-1，最终得到产物C-164:6.29g(收率：82％),MS(m/z)(M+):767。The method is the same as Example 1, except that B-164 (4.63 g, 10 mmol) replaces B-1, and the final product C-164 is 6.29 g (yield: 82%), MS (m/z) (M+): 767.
实施例28Embodiment 28
本实施例提供一种芳香胺化合物C-172，该芳香胺化合物的合成路线如下：
This embodiment provides an aromatic amine compound C-172, and the synthesis route of the aromatic amine compound is as follows:
方法同实施例1，区别在于，将B-172(3.71g，10mmol)替换B-1，最终得到产物C-172:4.73g(收率：70％),MS(m/z)(M+):675。The method is the same as Example 1, except that B-172 (3.71 g, 10 mmol) replaces B-1, and the final product C-172 is 4.73 g (yield: 70%), MS (m/z) (M+): 675.
实施例29Embodiment 29
本实施例提供一种芳香胺化合物C-180，该芳香胺化合物的合成路线如下：
This embodiment provides an aromatic amine compound C-180, and the synthesis route of the aromatic amine compound is as follows:
方法同实施例1，区别在于，将B-180(5.24g，10mmol)替换B-1，最终得到产物C-180:6.21g(收率：75％),MS(m/z)(M+):828。The method is the same as Example 1, except that B-180 (5.24 g, 10 mmol) is used to replace B-1, and the final product C-180 is 6.21 g (yield: 75%), MS (m/z) (M+): 828.
实施例30Embodiment 30
本实施例提供一种芳香胺化合物C-181，该芳香胺化合物的合成路线如下：
This embodiment provides an aromatic amine compound C-181, and the synthesis route of the aromatic amine compound is as follows:
方法同实施例1，区别在于，将B-181(5.24g，10mmol)替换B-1，最终得到产物C-181:6.46g(收率：78％),MS(m/z)(M+):828。The method is the same as Example 1, except that B-181 (5.24 g, 10 mmol) replaces B-1, and the final product C-181 is 6.46 g (yield: 78%), MS (m/z) (M+): 828.
实施例31Embodiment 31
本实施例提供一种芳香胺化合物C-186，该芳香胺化合物的合成路线如下：
This embodiment provides an aromatic amine compound C-186, and the synthesis route of the aromatic amine compound is as follows:
方法同实施例1，区别在于，将B-186(3.76g，10mmol)替换B-1，最终得到产物C-186:5.58g(收率：82％),MS(m/z)(M+):680。The method is the same as Example 1, except that B-186 (3.76 g, 10 mmol) is used to replace B-1, and the final product C-186 is 5.58 g (yield: 82%), MS (m/z) (M+): 680.
实施例32Embodiment 32
本实施例提供一种芳香胺化合物C-216，该芳香胺化合物的合成路线如下：
This embodiment provides an aromatic amine compound C-216, and the synthesis route of the aromatic amine compound is as follows:
方法同实施例1，区别在于，将B-216(4.72g，10mmol)替换B-1，最终得到产物C-216:5.51g(收率：71％),MS(m/z)(M+):776。The method is the same as Example 1, except that B-216 (4.72 g, 10 mmol) replaces B-1, and the final product C-216 is obtained: 5.51 g (yield: 71%), MS (m/z) (M+): 776.
实施例33Embodiment 33
本实施例提供一种芳香胺化合物C-219，该芳香胺化合物的合成路线如下：
This embodiment provides an aromatic amine compound C-219, and the synthesis route of the aromatic amine compound is as follows:
方法同实施例1，区别在于，将B-219(3.96g，10mmol)替换B-1，最终得到产物C-219:5.11g(收率：73％),MS(m/z)(M+):700。The method is the same as Example 1, except that B-219 (3.96 g, 10 mmol) replaces B-1, and finally the product C-219 is obtained: 5.11 g (yield: 73%), MS (m/z) (M+): 700.
实施例34Embodiment 34
本实施例提供一种芳香胺化合物C-221，该芳香胺化合物的合成路线如下：
This embodiment provides an aromatic amine compound C-221, and the synthesis route of the aromatic amine compound is as follows:
方法同实施例1，区别在于，将B-221(4.72g，10mmol)替换B-1，最终得到产物C-221:6.44g(收率：83％),MS(m/z)(M+):776。The method is the same as Example 1, except that B-221 (4.72 g, 10 mmol) replaces B-1, and the final product C-221 is obtained: 6.44 g (yield: 83%), MS (m/z) (M+): 776.
实施例35Embodiment 35
本实施例提供一种芳香胺化合物C-227，该芳香胺化合物的合成路线如下：
This embodiment provides an aromatic amine compound C-227, and the synthesis route of the aromatic amine compound is as follows:
方法同实施例1，区别在于，将B-227(4.12g，10mmol)替换B-1，最终得到产物C-227:5.66g(收率：79％),MS(m/z)(M+):716。The method is the same as Example 1, except that B-227 (4.12 g, 10 mmol) replaces B-1, and finally the product C-227 is obtained: 5.66 g (yield: 79%), MS (m/z) (M+): 716.
实施例36Embodiment 36
本实施例提供一种芳香胺化合物C-228，该芳香胺化合物的合成路线如下：
This embodiment provides an aromatic amine compound C-228, and the synthesis route of the aromatic amine compound is as follows:
方法同实施例1，区别在于，将B-228(5.00g，10mmol)替换B-1，最终得到产物C-228:6.76g(收率：84％),MS(m/z)(M+):805。The method is the same as Example 1, except that B-228 (5.00 g, 10 mmol) replaces B-1, and the final product C-228 is 6.76 g (yield: 84%), MS (m/z) (M+): 805.
实施例37Embodiment 37
本实施例提供一种芳香胺化合物C-237，该芳香胺化合物的合成路线如下：
This embodiment provides an aromatic amine compound C-237, and the synthesis route of the aromatic amine compound is as follows:
方法同实施例1，区别在于，将B-237(4.11g，10mmol)替换B-1，最终得到产物C-237:5.65g(收率：79％),MS(m/z)(M+):715。The method is the same as Example 1, except that B-237 (4.11 g, 10 mmol) replaces B-1, and finally the product C-237 is obtained: 5.65 g (yield: 79%), MS (m/z) (M+): 715.
实施例38Embodiment 38
本实施例提供一种芳香胺化合物C-255，该芳香胺化合物的合成路线如下：
This embodiment provides an aromatic amine compound C-255, and the synthesis route of the aromatic amine compound is as follows:
方法同实施例1，区别在于，将B-255(4.96g，10mmol)替换B-1，最终得到产物C-255:6.56g(收率：82％),MS(m/z)(M+):800。The method is the same as Example 1, except that B-255 (4.96 g, 10 mmol) replaces B-1, and the final product C-255 is 6.56 g (yield: 82%), MS (m/z) (M+): 800.
实施例39Embodiment 39
本实施例提供一种芳香胺化合物C-278，该芳香胺化合物的合成路线如下：
This embodiment provides an aromatic amine compound C-278, and the synthesis route of the aromatic amine compound is as follows:
方法同实施例1，区别在于，将B-278(3.71g，10mmol)替换B-1，最终得到产物C-278:5.21g(收率：77％),MS(m/z)(M+):676。The method is the same as Example 1, except that B-278 (3.71 g, 10 mmol) replaces B-1, and the final product C-278 is 5.21 g (yield: 77%), MS (m/z) (M+): 676.
实施例40Embodiment 40
本实施例提供一种芳香胺化合物C-283，该芳香胺化合物的合成路线如下：
This embodiment provides an aromatic amine compound C-283, and the synthesis route of the aromatic amine compound is as follows:
方法同实施例1，区别在于，将B-283(3.81g，10mmol)替换B-1，最终得到产物C-283:4.86g(收率：71％),MS(m/z)(M+):685。The method is the same as Example 1, except that B-283 (3.81 g, 10 mmol) replaces B-1, and finally the product C-283 is obtained: 4.86 g (yield: 71%), MS (m/z) (M+): 685.
实施例41Embodiment 41
本实施例提供一种芳香胺化合物C-299，该芳香胺化合物的合成路线如下：
This embodiment provides an aromatic amine compound C-299, and the synthesis route of the aromatic amine compound is as follows:
方法同实施例1，区别在于，将B-299(5.13g，10mmol)替换B-1，最终得到产物C-299:6.70g(收率：82％),MS(m/z)(M+):817。The method is the same as Example 1, except that B-299 (5.13 g, 10 mmol) replaces B-1, and the final product C-299 is 6.70 g (yield: 82%), MS (m/z) (M+): 817.
对比例1Comparative Example 1
本对比例提供了研究过程中实验过的一种化合物D1，其具体的结构式为：
This comparative example provides a compound D1 that has been tested during the research process, and its specific structural formula is:
对比例2Comparative Example 2
本对比例提供了研究过程中实验过的一种化合物D2，其具体的结构式为：
This comparative example provides a compound D2 that has been tested during the research process, and its specific structural formula is:
对比例3Comparative Example 3
本对比例提供了研究过程中实验过的一种化合物D3，其具体的结构式为：
This comparative example provides a compound D3 that has been tested during the research process, and its specific structural formula is:
效果例1Effect Example 1
能级评价Energy level evaluation
为了说明本发明提供的芳香胺化合物的分子构型、电子云分布及能级特性，使用Gaussian 09W软件，基于密度泛函理论(DFT)计算方法(基组水平设置为：6-311+G(2d,p)，电荷数为0)，选取C-1、C-2、C-3、C-4、C-11、C-20、C-29、C-52、C-53、C-73、C-111、C-121、C-131、C-172、C-180、C-186、C-227、C-228、C-237、C-299、D1、D2以及D3的分子结构进行几何优化(Optimization)，最终得到了分子几何构型和前沿分子轨道分布及相关能级理论参数如下表1所示：In order to illustrate the molecular configuration, electron cloud distribution and energy level characteristics of the aromatic amine compound provided by the present invention, Gaussian 09W software was used based on the density functional theory (DFT) calculation method (the basis set level was set to: 6-311+G(2d,p), and the charge number was 0), and the molecular structures of C-1, C-2, C-3, C-4, C-11, C-20, C-29, C-52, C-53, C-73, C-111, C-121, C-131, C-172, C-180, C-186, C-227, C-228, C-237, C-299, D1, D2 and D3 were selected for geometric optimization. Finally, the molecular geometric configuration, frontier molecular orbital distribution and related energy level theoretical parameters were obtained as shown in Table 1 below:
表1

Table 1

由表1的数据可知，与对比例化合物相比本发明提供的芳香胺化合物具有相对较大的能隙值、相对较高的LUMO值和相对较大的T1，将本发明提供的芳香胺化合物用作空穴传输层材料或发光辅助层材料，其能级与邻近有机层的能级更加匹配，能够阻挡电子或激子离开发光层；另外，由表1的数据还可以看出本发明提供的芳香胺化合物的分子量主要在700-850之间，个别含有较多稠环结构的化合物的分子量能够达到850以上，这是因为本发明提供的芳香胺化合物具有相对较大的分子量，该母核中四联苯的分子量占整个芳香胺化合物的分子量的35％以上，该芳香胺化合物具有相对较高的玻璃化转变温度和热稳定性，避免后期为提高Tg而引入其他不必要的大分子量片段，因此，本发明提供的芳香胺化合物能够满足有机电致发光器件对空穴传输层或发光辅助层的要求。It can be seen from the data in Table 1 that the aromatic amine compound provided by the present invention has a relatively large energy gap value, a relatively high LUMO value and a relatively large T1 compared with the comparative example compound. The aromatic amine compound provided by the present invention is used as a hole transport layer material or a luminescent auxiliary layer material, and its energy level is more matched with the energy level of the adjacent organic layer, which can block electrons or excitons from leaving the luminescent layer; in addition, it can be seen from the data in Table 1 that the molecular weight of the aromatic amine compound provided by the present invention is mainly between 700 and 850, and the molecular weight of some compounds containing more condensed ring structures can reach more than 850. This is because the aromatic amine compound provided by the present invention has a relatively large molecular weight, and the molecular weight of the quaternary biphenyl in the parent core accounts for more than 35% of the molecular weight of the entire aromatic amine compound. The aromatic amine compound has a relatively high glass transition temperature and thermal stability, avoiding the introduction of other unnecessary large molecular weight fragments in order to increase Tg in the later stage. Therefore, the aromatic amine compound provided by the present invention can meet the requirements of the organic electroluminescent device for the hole transport layer or the luminescent auxiliary layer.
器件实施例Device Embodiment
以下实施例的有机电致发光器件包括依次设置在衬底基板1上的阳极2、空穴传输区、发光层5、电子传输区、阴极8；其中，空穴传输区包括空穴传输层3和发光辅助层4；电子传输区包括电子传输层6和电子注入层7；发光层5为主体和掺杂客体组成，发光层主体可以为一种分子材料组成或多种分子材料组成。有机电致发光器件的典型结构如图1所示。The organic electroluminescent device of the following embodiment includes an anode 2, a hole transport region, a light-emitting layer 5, an electron transport region, and a cathode 8, which are sequentially arranged on a substrate 1; wherein the hole transport region includes a hole transport layer 3 and a light-emitting auxiliary layer 4; the electron transport region includes an electron transport layer 6 and an electron injection layer 7; the light-emitting layer 5 is composed of a host and a doped guest, and the host of the light-emitting layer can be composed of one molecular material or multiple molecular materials. The typical structure of an organic electroluminescent device is shown in FIG1 .
以下实施例的阳极采用本领域内常用的阳极材料，如ITO、Ag或其多层结构。空穴注入单元采用本领域内常用的空穴注入材料，同时加入F4TCNQ、HATCN、NDP-9等进行掺杂。空穴传输单元采用本领域内常用的空穴传输材料。发光单元采用本领域内常用的发光材料，例如可以由主体材料和发射的客体材料掺杂构成，发射的客体材料可以为有机材料如芘类化合物，也可以为金属配合物(如金属Ir，Pt等)。电子传输单元采用本领域内常用的电子传输材料。电子注入层采用本领域内常用的电子注入材料，如Liq、LiF、Yb等。阴极采用本领域内常用材料，如金属Al、Ag或金属混合物(Ag掺杂的Mg、Ag掺杂的Ca等)。The anode of the following embodiments adopts anode materials commonly used in the art, such as ITO, Ag or their multilayer structures. The hole injection unit adopts hole injection materials commonly used in the art, and F4TCNQ, HATCN, NDP-9, etc. are added for doping. The hole transport unit adopts hole transport materials commonly used in the art. The light-emitting unit adopts light-emitting materials commonly used in the art, for example, it can be composed of a host material and an emitted guest material doped, and the emitted guest material can be an organic material such as a pyrene compound, or it can be a metal complex (such as metal Ir, Pt, etc.). The electron transport unit adopts electron transport materials commonly used in the art. The electron injection layer adopts electron injection materials commonly used in the art, such as Liq, LiF, Yb, etc. The cathode adopts materials commonly used in the art, such as metal Al, Ag or metal mixtures (Ag-doped Mg, Ag-doped Ca, etc.).
以下实施例中的电极制备方法和各功能层的沉积方法均为本领域常规方法，例如真空热蒸镀或喷墨打印等，在此不再赘述，仅对制备过程中的一些工艺细节、测试方法补充说明如下：The electrode preparation methods and the deposition methods of each functional layer in the following embodiments are conventional methods in the art, such as vacuum thermal evaporation or inkjet printing, etc., which will not be described in detail here. Only some process details and test methods in the preparation process are supplemented as follows:
红光器件实施例1Red light device embodiment 1
本实施例提供一种红光有机电致发光器件，其制备方法为：首先在形成于基板的ITO层(阳极)上，以10nm的厚度真空沉积HTL和F4TCNQ(HTL与F4TCNQ的质量比为97:3)形成空穴注入层；其次在上述空穴注入层上，以120nm的厚度真空沉积HTL形成空穴传输层，其次在上述空穴传输层上，以80nm的厚度真空沉积C-1形成发光辅助层；再次在上述发光辅助层上，以40nm的厚度真空沉积RH与RD的混合物形成发光层，其中RH作为主体、RD作为掺杂剂，主体与掺杂剂的质量比为97:3；接着在上述发光层上，以35nm的厚度真空沉积ET-01与Liq的混合物形成电子传输层，其中ET-01与Liq的质量比为1：1；然后在上述电子传输层上，以0.2nm的厚度沉积LiF形成电子注入层，最后在上述电子注入层上，以150nm的厚度沉积铝(Al)形成阴极，制备出红光有机电致发光器件。除发光辅助层外， 其余各层材料的分子结构式如下：
The present embodiment provides a red light organic electroluminescent device, and the preparation method thereof is as follows: first, on the ITO layer (anode) formed on the substrate, HTL and F4TCNQ (the mass ratio of HTL to F4TCNQ is 97:3) are vacuum deposited with a thickness of 10 nm to form a hole injection layer; secondly, on the hole injection layer, HTL is vacuum deposited with a thickness of 120 nm to form a hole transport layer; secondly, on the hole transport layer, C-1 is vacuum deposited with a thickness of 80 nm to form a light-emitting auxiliary layer; thirdly, on the light-emitting auxiliary layer, C-1 is vacuum deposited with a thickness of 40 nm to form a light-emitting auxiliary layer; The mixture of RH and RD forms a light-emitting layer, wherein RH is the main body and RD is the dopant, and the mass ratio of the main body to the dopant is 97:3; then on the light-emitting layer, a mixture of ET-01 and Liq is vacuum deposited with a thickness of 35nm to form an electron transport layer, wherein the mass ratio of ET-01 to Liq is 1:1; then on the electron transport layer, LiF is deposited with a thickness of 0.2nm to form an electron injection layer, and finally on the electron injection layer, aluminum (Al) is deposited with a thickness of 150nm to form a cathode, and a red light organic electroluminescent device is prepared. In addition to the light-emitting auxiliary layer, The molecular structures of the remaining layers of materials are as follows:
红光器件实施例2-10Red light device embodiment 2-10
本实施例提供一种红光有机电致发光器件，其制备方法为：将红光器件实施例1中的化合物C-1分别置换为化合物C-4、C-9、C-11、C-14、C-20、C-52、C-53、C-73以及C-84形成发光辅助层，其他制备步骤与红光器件实施例1相同，分别制备出红光有机电致发光器件。This embodiment provides a red light organic electroluminescent device, and its preparation method is as follows: the compound C-1 in the red light device embodiment 1 is replaced by compounds C-4, C-9, C-11, C-14, C-20, C-52, C-53, C-73 and C-84 to form a light-emitting auxiliary layer, and the other preparation steps are the same as those in the red light device embodiment 1, and red light organic electroluminescent devices are prepared respectively.
红光器件对比例1Red light device comparative example 1
本对比例提供了研究过程中实验过的一种红光有机电致发光器件，其制备方法为：将红光器件实施例1中的化合物C1置换为对比化合物D1形成发光辅助层，其他制备步骤与红光器件实施例1相同，制备出红光有机电致发光器件。This comparative example provides a red light organic electroluminescent device that was experimented during the research process. The preparation method thereof is as follows: Compound C1 in Example 1 of the red light device is replaced by comparative compound D1 to form a light-emitting auxiliary layer, and the other preparation steps are the same as those in Example 1 of the red light device to prepare a red light organic electroluminescent device.
绿光器件实施例1Green light device embodiment 1
本实施例提供一种绿光有机电致发光器件，其制备方法为：首先在形成于基板的ITO层(阳极)上，以10nm的厚度真空沉积HTL和F4TCNQ(HTL与F4TCNQ的质量比为97:3)形成空穴注入层；其次在上述空穴注入层上，以120nm的厚度真空沉积HTL形成空穴传输层，其次在上述空穴传输层上，以30nm的厚度真空沉积C-111形成发光辅助层；再次在上述发光辅助层上，以35nm的厚度真空沉积GPH、GNH与GD的混合物形成发光层，其中GPH与GNH以4:6的质量比混合均匀后作为主体、GD作为掺杂剂，主体与掺杂剂的质量比为95:5；接着在上述发光层上，以35nm的厚度真空沉积ET-01与Liq的混合物形成电子传输层，其中ET-01与Liq的质量比为1：1；然后在上述电子传输层上，以0.2nm的厚度沉积LiF形成电子注入层，最后在上述电子注入层上，以150nm的厚度沉积铝(Al)形成阴极，制备出绿光有机电致发光器件。除发光辅助层外，其余各层材料的分子结构式如下：
The present embodiment provides a green light organic electroluminescent device, and the preparation method thereof is as follows: first, on the ITO layer (anode) formed on the substrate, HTL and F4TCNQ (the mass ratio of HTL to F4TCNQ is 97:3) are vacuum deposited with a thickness of 10 nm to form a hole injection layer; secondly, on the hole injection layer, HTL is vacuum deposited with a thickness of 120 nm to form a hole transport layer; secondly, on the hole transport layer, C-111 is vacuum deposited with a thickness of 30 nm to form a light-emitting auxiliary layer; thirdly, on the light-emitting auxiliary layer, GPH, GNH and GD are vacuum deposited with a thickness of 35 nm. The mixture forms a light-emitting layer, wherein GPH and GNH are mixed evenly at a mass ratio of 4:6 as the main body, GD is used as the dopant, and the mass ratio of the main body to the dopant is 95:5; then on the above-mentioned light-emitting layer, a mixture of ET-01 and Liq is vacuum deposited at a thickness of 35nm to form an electron transport layer, wherein the mass ratio of ET-01 to Liq is 1:1; then on the above-mentioned electron transport layer, LiF is deposited at a thickness of 0.2nm to form an electron injection layer, and finally on the above-mentioned electron injection layer, aluminum (Al) is deposited at a thickness of 150nm to form a cathode, and a green light organic electroluminescent device is prepared. Except for the light-emitting auxiliary layer, the molecular structure formula of the remaining layers of materials is as follows:
绿光器件实施例2-10Green light device embodiment 2-10
本实施例提供一种绿光有机电致发光器件，其制备方法为：将绿光器件实施例1中的化合物C-111分别置换为化合物C-115、C-121、C-131、C-133、C-164、C-172、C-180、C-181以及C-186形成发光辅助层，其他制备步骤与绿光器件实施例1相同，分别制备出绿光有机电致发光器件。This embodiment provides a green light organic electroluminescent device, and its preparation method is as follows: the compound C-111 in the green light device embodiment 1 is replaced by compounds C-115, C-121, C-131, C-133, C-164, C-172, C-180, C-181 and C-186 to form a luminescent auxiliary layer, and the other preparation steps are the same as those in the green light device embodiment 1, and green light organic electroluminescent devices are prepared respectively.
绿光器件对比例1Green light device comparative example 1
本对比例提供了研究过程中实验过的一种绿光有机电致发光器件，其制备方法为：将绿光器件实施例1中的化合物C-111置换为对比化合物D2形成发光辅助层，其他制备步骤与绿光器件实施例1相同，制备出绿光有机电致发光器件。This comparative example provides a green organic electroluminescent device that has been experimented during the research process. The preparation method thereof is as follows: the compound C-111 in the green light device example 1 is replaced with the comparative compound D2 to form a luminescent auxiliary layer, and the other preparation steps are the same as those in the green light device example 1 to prepare a green organic electroluminescent device.
蓝光器件实施例1Blue light device embodiment 1
本实施例提供一种蓝光有机电致发光器件，其制备方法为：首先在形成于基板的ITO层(阳极)上，以10nm的厚度真空沉积HTL和F4TCNQ(HTL与F4TCNQ的质量比为97:3)形成空穴注入层；其次在上述空穴注入层上，以120nm的厚度真空沉积HTL形成空穴传输层，其次在上述空穴传输层上，以10nm的厚度真空沉积C-216形成发光辅助层；再次在上述发光辅助层上，以20nm的厚度真空沉积BH与BD的混合物形成发光层，其中BH作为主体、BD作为掺杂剂，主体与掺杂剂的质量比为98:2；接着在上述发光层上，以35nm的厚度真空沉积ET-01与Liq的混合物形成电子传输层；然后在上述电子传输层上，以0.2nm的厚度沉积LiF形成电子注入层，最后在上述电子注入层上，以150nm的厚度沉积铝(Al)形成阴极，制备出蓝光有机电致发光器件。除发光辅助层外，其余各层材料的分子结构式如下：
The present embodiment provides a blue light organic electroluminescent device, and the preparation method thereof is as follows: first, on the ITO layer (anode) formed on the substrate, HTL and F4TCNQ (the mass ratio of HTL to F4TCNQ is 97:3) are vacuum deposited with a thickness of 10 nm to form a hole injection layer; secondly, on the hole injection layer, HTL is vacuum deposited with a thickness of 120 nm to form a hole transport layer; secondly, on the hole transport layer, C-216 is vacuum deposited with a thickness of 10 nm to form a light-emitting auxiliary layer; thirdly, on the light-emitting auxiliary layer, A mixture of BH and BD was vacuum deposited at a thickness of 20nm to form a light-emitting layer, wherein BH was used as a host and BD was used as a dopant, and the mass ratio of the host to the dopant was 98:2; then, a mixture of ET-01 and Liq was vacuum deposited at a thickness of 35nm on the light-emitting layer to form an electron transport layer; then, LiF was deposited at a thickness of 0.2nm on the electron transport layer to form an electron injection layer, and finally, aluminum (Al) was deposited at a thickness of 150nm on the electron injection layer to form a cathode, thereby preparing a blue light organic electroluminescent device. Except for the light-emitting auxiliary layer, the molecular structure formulas of the remaining materials are as follows:
蓝光器件实施例2-10Blue light device embodiment 2-10
本实施例提供一种蓝光有机电致发光器件，其制备方法为：将蓝光器件实施例1中的化合物C-216分别置换为化合物C-219、C-221、C-227、C-228、C-237、C-255、C-278、C-283以及C-299形成发光辅助层，其他制备步骤与蓝光器件实施例1相同，分别制备出蓝光有机电致发光器件。This embodiment provides a blue light organic electroluminescent device, and its preparation method is as follows: the compound C-216 in the blue light device embodiment 1 is replaced by compounds C-219, C-221, C-227, C-228, C-237, C-255, C-278, C-283 and C-299 to form a luminescent auxiliary layer, and the other preparation steps are the same as those in the blue light device embodiment 1, and blue light organic electroluminescent devices are prepared respectively.
蓝光器件实施例11-20Blue light device embodiments 11-20
本实施例提供一种蓝光有机电致发光器件，其制备方法为：将蓝光器件实施例1中的化合物C-216置换为P-1形成发光辅助层，将蓝光器件实施例1中的空穴传输层材料分别替换为化合物C-2、C-3、C-16、C-17、C-21、C-22、C-23、C-26、C-29以及C-31，其他制备步骤与蓝光器件实施例1相同，分别制备出蓝光有机电致发光器件。This embodiment provides a blue light organic electroluminescent device, and its preparation method is as follows: the compound C-216 in the blue light device embodiment 1 is replaced by P-1 to form a light-emitting auxiliary layer, and the hole transport layer materials in the blue light device embodiment 1 are replaced by compounds C-2, C-3, C-16, C-17, C-21, C-22, C-23, C-26, C-29 and C-31 respectively, and the other preparation steps are the same as those in the blue light device embodiment 1, and blue light organic electroluminescent devices are prepared respectively.
蓝光器件对比例1Blue light device comparative example 1
本对比例提供了研究过程中实验过的一种蓝光有机电致发光器件，其制备方法为：将蓝光器件实施例1中的化合物C-216置换为对比化合物D3形成发光辅助层，其他制备方法与蓝光器件实施例1相同，制备出蓝光有机电致发光器件。This comparative example provides a blue light organic electroluminescent device that was experimented during the research process. The preparation method thereof is: replacing the compound C-216 in the blue light device embodiment 1 with the comparative compound D3 to form a luminescent auxiliary layer, and the other preparation methods are the same as those in the blue light device embodiment 1 to prepare a blue light organic electroluminescent device.
蓝光器件对比例2Blue light device comparative example 2
本对比例提供了研究过程中实验过的一种蓝光有机电致发光器件，其制备方法为：将蓝光器件实施例1中的化合物C-216置换为P-1形成发光辅助层，其他制备步骤与蓝光器件实施例1相同，制备出蓝光有机电致发光器件。This comparative example provides a blue light organic electroluminescent device that has been experimented during the research process. The preparation method thereof is as follows: the compound C-216 in the blue light device embodiment 1 is replaced by P-1 to form a luminescent auxiliary layer, and the other preparation steps are the same as those in the blue light device embodiment 1 to prepare a blue light organic electroluminescent device.
效果例Effect example
将红光器件实施例1-10、红光器件对比例1、绿光器件实施例1-10、绿光器件对比例1、蓝光器件实施例1-20以及蓝光器件对比例1-2提供的有机电致发光器件进行标准方法测试，在J＝10mA/cm2的电流密度下确定有机电致发光器件的驱动电压，亮度，电致发光电流效率(以cd/A计量)和外量子效率(EQE，以百分比计量)，其作为发光密度的函数从呈现郎伯发射特性的电流/电压/发光密度特性线(IVL特性线)进行计算，发光光谱。将寿命LT定义为如下的时间，在恒定电流J下工作时，亮度在该时间后从初始发光亮度L0降至特定的比例L1；J＝50mA/cm2和L1＝90％的表述是指在50mA/cm2下工作时，发光亮度在时间LT之后降至其初始值L0的90％，类似地，J＝20mA/cm2，L1＝80％是指，在20mA/cm2下工作时，发光 亮度在时间LT之后降至其初始值L0的80％。The organic electroluminescent devices provided by red light device embodiments 1-10, red light device comparison example 1, green light device embodiments 1-10, green light device comparison example 1, blue light device embodiments 1-20 and blue light device comparison example 1-2 were tested by standard methods, and the driving voltage, brightness, electroluminescent current efficiency (measured in cd/A) and external quantum efficiency (EQE, measured in percentage) of the organic electroluminescent devices were determined at a current density of J=10mA/ cm2 , which were calculated as a function of luminous density from the current/voltage/luminous density characteristic line (IVL characteristic line) exhibiting Lambertian emission characteristics, and the luminescent spectrum. The lifetime LT is defined as the time after which the brightness decreases from the initial brightness L0 to a specific ratio L1 when operating at a constant current J; the expression J=50mA/ cm2 and L1 =90% means that when operating at 50mA/ cm2 , the brightness decreases to 90% of its initial value L0 after the time LT. Similarly, J=20mA/ cm2 , L1 =80% means that when operating at 20mA/ cm2 , the brightness decreases to 90% of its initial value L0 after the time LT. The brightness drops to 80% of its initial value L 0 after time LT.
将红光器件实施例1-10、红光器件对比例1、绿光器件实施例1-10、绿光器件对比例1、蓝光器件实施例1-20以及蓝光器件对比例1-2提供的有机电致发光器件进行性能测试，具体的测试仪器及方法如下：亮度使用光谱扫描仪PhotoResearch PR-635测试；电流密度和起亮电压：使用数字源表Keithley 2400测试；寿命测试：使用LT-96ch寿命测试装置；具体测试结果如表2-表5所示：The organic electroluminescent devices provided by the red light device embodiments 1-10, the red light device comparative example 1, the green light device embodiments 1-10, the green light device comparative example 1, the blue light device embodiments 1-20 and the blue light device comparative example 1-2 were subjected to performance tests. The specific testing instruments and methods are as follows: the brightness was tested using a spectrum scanner PhotoResearch PR-635; the current density and the light-on voltage were tested using a digital source meter Keithley 2400; the life test was performed using an LT-96ch life test device; the specific test results are shown in Tables 2 to 5:
表2红光器件性能测试结果
Table 2 Red light device performance test results
表3绿光器件性能测试结果
Table 3 Green light device performance test results
表4蓝光器件性能测试结果

Table 4 Blue light device performance test results

表5蓝光器件性能测试结果
Table 5 Blue light device performance test results
由表2-表5的器件性能测试结果可知，与对比化合物相比，使用本发明提供的芳香胺化合物作为空穴传输层材料或发光辅助层所制备的有机电致发光器件的驱动电压明显降低，发光效率显著提高，寿命明显延长，推测其原因为：本发明提供的芳香胺化合物含有特殊连接方式的四联苯结构，四联苯中与氮连接的苯的3号位置与5号位置分别被单苯和二联苯取代，该特殊的连接方式使得本发明所提供的芳香胺化合物具有相对较高的LUMO和能隙值，将本发明提供的芳香胺化合物作为空穴传输层材料或发光辅助层材料，该空穴传输层材料或发光辅助层材料与邻近有机层的能级更加匹配，且能够阻挡电子或激子离开发光层，因此能够有效降低有机电致发光器件的驱动电压、提高器件的效率；该特殊的连接方式使得本发明所提供的芳香胺化合物具有适宜程度的共轭，因此具有相对较高的T1值，将本发明提供的芳香胺化合物作为空穴传输层材料或发光辅助层材料，该空穴传输层或发光辅助层的载流子所传递的能量能够满足发光层跃迁所需的发光能量，因此能够显著提高有机电致发光器件的发光效率；本发明提供的芳香胺化合物的分子量在大于650，能够避免玻璃化转变温度过低，抑制材料的分解，进而能够有效提高器件寿命。由此说明本发明所提供的芳香胺化合物是性能良好的空穴传输层材料或发光辅助层材料，能够满足有机电致发光器件的性能要求，具有实用价值。It can be seen from the device performance test results in Tables 2 to 5 that, compared with the comparative compounds, the driving voltage of the organic electroluminescent device prepared by using the aromatic amine compound provided by the present invention as the hole transport layer material or the luminescent auxiliary layer is significantly reduced, the luminescent efficiency is significantly improved, and the life is significantly prolonged. It is speculated that the reason is that the aromatic amine compound provided by the present invention contains a quaternary phenyl structure with a special connection mode, and the 3rd position and the 5th position of the benzene connected to nitrogen in the quaternary phenyl are replaced by monophenyl and diphenyl respectively. This special connection mode makes the aromatic amine compound provided by the present invention have a relatively high LUMO and energy gap value. When the aromatic amine compound provided by the present invention is used as a hole transport layer material or a luminescent auxiliary layer material, the hole transport layer material or the luminescent auxiliary layer material is connected to the adjacent organic The energy level of the layer is more matched, and it can block electrons or excitons from leaving the light-emitting layer, so it can effectively reduce the driving voltage of the organic electroluminescent device and improve the efficiency of the device; this special connection method makes the aromatic amine compound provided by the present invention have an appropriate degree of conjugation, so it has a relatively high T1 value. The aromatic amine compound provided by the present invention is used as a hole transport layer material or a light-emitting auxiliary layer material. The energy transferred by the carriers of the hole transport layer or the light-emitting auxiliary layer can meet the light-emitting energy required for the transition of the light-emitting layer, so it can significantly improve the luminous efficiency of the organic electroluminescent device; the molecular weight of the aromatic amine compound provided by the present invention is greater than 650, which can avoid the glass transition temperature being too low, inhibit the decomposition of the material, and then effectively improve the device life. This shows that the aromatic amine compound provided by the present invention is a hole transport layer material or a light-emitting auxiliary layer material with good performance, which can meet the performance requirements of organic electroluminescent devices and has practical value.
显然，本发明的上述实施例仅仅是为清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定，对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动，这里无法对所有的实施方式予以穷举，凡是属于本发明的技术方案所引伸出的显而易见的变化或变动仍处于本发明的保护范围之列。 Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not limitations on the implementation methods of the present invention. For ordinary technicians in the relevant field, other different forms of changes or modifications can be made based on the above description. It is impossible to list all the implementation methods here. All obvious changes or modifications derived from the technical solution of the present invention are still within the protection scope of the present invention.

Claims (9)

  1. 一种包含四联苯结构的芳香胺化合物，其特征在于，所述芳香胺化合物的结构式如式Ⅰ所示：
    An aromatic amine compound containing a quaternary phenyl structure, characterized in that the structural formula of the aromatic amine compound is as shown in Formula I:
    其中，所述Ar1、Ar2各自独立地选自取代或未取代的C6～C60的芳基、取代或未取代的C5～C60的杂芳基、取代或未取代的C10～C60的稠环芳基、取代或未取代的C9～C60的杂稠环芳基、取代或未取代的C3～C30的环烷基中的任意一种；Wherein, Ar 1 and Ar 2 are each independently selected from any one of a substituted or unsubstituted C 6 ～C 60 aryl group, a substituted or unsubstituted C 5 ～C 60 heteroaryl group, a substituted or unsubstituted C 10 ～C 60 condensed ring aryl group, a substituted or unsubstituted C 9 ～C 60 heterocondensed ring aryl group, and a substituted or unsubstituted C 3 ～C 30 cycloalkyl group;
    当所述Ar1或Ar2存在取代基时，所述取代基选自氘、卤素、羟基、氰基、硝基、氨基、羧基或其盐、磺酸基或其盐、磷酸基或其盐、C1～C10的烷基、C6～C60的芳基、C5～C60的杂芳基、C10～C60的稠环芳基、C9～C60的杂稠环芳基或C3～C30的环烷基中的任意一种，其中两个或两个以上的取代基可以相同或不同，可以彼此连接形成脂肪环、芳环、杂芳环、稠环或杂稠环；When Ar1 or Ar2 has a substituent, the substituent is selected from any one of deuterium, halogen, hydroxyl, cyano, nitro, amino, carboxyl or its salt, sulfonic acid or its salt, phosphate or its salt, C1 - C10 alkyl, C6 - C60 aryl , C5 -C60 heteroaryl, C10 - C60 condensed ring aryl, C9 - C60 heterocondensed ring aryl or C3 - C30 cycloalkyl, wherein two or more substituents may be the same or different, and may be connected to each other to form an aliphatic ring, an aromatic ring, a heteroaromatic ring, a condensed ring or a heterocondensed ring;
    所述L2选自单键、取代或未取代的C1～C12的亚烷基、取代或未取代的C6～C30的亚芳基、取代或未取代的C6～C30的亚杂芳基中的任意一种；The L2 is selected from any one of a single bond, a substituted or unsubstituted C1 - C12 alkylene group, a substituted or unsubstituted C6 - C30 arylene group, and a substituted or unsubstituted C6 - C30 heteroarylene group;
    所述式I所示化合物上的任意一个氢可以各自独立地被氘、烷基或环烷基取代。Any hydrogen on the compound of formula I can be independently replaced by deuterium, alkyl or cycloalkyl.
  2. 根据权利要求1所述的芳香胺化合物，其特征在于，所述Ar1的结构式如式Ⅱ所示：
    The aromatic amine compound according to claim 1, characterized in that the structural formula of Ar 1 is as shown in Formula II:
    其中，所述R1、R2各自独立地选自氢、氘、取代或未取代的C1～C10的烷基、取代或未取代的C3～C10的环烷基、取代或未取代的C6～C30的芳基、取代或未取代的C5～C30的杂芳基、取代或未取代的C1～C6的烷氧基、取代或未取代的C10～C60的稠环基、取代或未取代的C9～C30的芳烷基、取代或未取代的C6～C30的芳氧基、取代或未取代的C6～C30芳胺基中的任意一种，上述任意两个或两个以上的基团可以彼此连接形成脂肪环、芳环、杂芳环、稠环或杂稠环；Wherein, R 1 and R 2 are each independently selected from any one of hydrogen, deuterium, substituted or unsubstituted C 1 to C 10 alkyl, substituted or unsubstituted C 3 to C 10 cycloalkyl, substituted or unsubstituted C 6 to C 30 aryl, substituted or unsubstituted C 5 to C 30 heteroaryl, substituted or unsubstituted C 1 to C 6 alkoxy, substituted or unsubstituted C 10 to C 60 condensed ring, substituted or unsubstituted C 9 to C 30 aralkyl, substituted or unsubstituted C 6 to C 30 aryloxy, substituted or unsubstituted C 6 to C 30 arylamine, and any two or more of the above groups can be connected to form an aliphatic ring, an aromatic ring, a heteroaromatic ring, a condensed ring or a heterocondensed ring;
    所述a选自1至5的整数；所述b选自1至4的整数；The a is selected from an integer from 1 to 5; the b is selected from an integer from 1 to 4;
    所述L1选自单键、O、S、取代或未取代的C1～C12的亚烷基、取代或未取代的C6～C30的亚芳基中的任意一种；The L1 is selected from any one of a single bond, O, S, a substituted or unsubstituted C1 - C12 alkylene group, and a substituted or unsubstituted C6 - C30 arylene group;
    所述式Ⅱ所示化合物上的任意一个氢可以各自独立地被氘、烷基或环烷基取代。Any hydrogen on the compound represented by formula II can be independently replaced by deuterium, alkyl or cycloalkyl.
  3. 根据权利要求2所述的芳香胺化合物，其特征在于，所述式Ⅱ所示的化合物为下述式Ⅱ-1～式Ⅱ-7所示结构中的一种：
    The aromatic amine compound according to claim 2, characterized in that the compound represented by formula II is one of the structures represented by the following formula II-1 to formula II-7:
    其中，所述n选自1至4的整数；所述m选自1至3的整数；Wherein, n is selected from an integer from 1 to 4; m is selected from an integer from 1 to 3;
    所述L1选自单键、O、S、取代或未取代的C1～C12的亚烷基、取代或未取代的C6～C30的亚芳基中的任意一种；The L1 is selected from any one of a single bond, O, S, a substituted or unsubstituted C1 - C12 alkylene group, and a substituted or unsubstituted C6 - C30 arylene group;
    所述L2选自单键、O、S中的任意一种；The L2 is selected from any one of a single bond, O, and S;
    所述X选自O、S、CR3R4、NR5中的任意一种；The X is selected from any one of O, S, CR 3 R 4 and NR 5 ;
    所述R3、R4各自独立地选自氢、氘、取代或未取代的C1～C10的烷基、取代或未取代的C6～C30的芳基、取代或未取代的C5～C30的杂芳基、取代或未取代的C10～C60的稠环基、取代或未取代的C6～C30的芳烷基、取代或未取代的C6～C30的芳氧基、取代或未取代的C6～C30芳硫基，R3、R4可以彼此连接形成脂肪环、芳环、杂芳环、稠环或杂稠环；Said R 3 and R 4 are each independently selected from hydrogen, deuterium, substituted or unsubstituted C 1 to C 10 alkyl, substituted or unsubstituted C 6 to C 30 aryl, substituted or unsubstituted C 5 to C 30 heteroaryl, substituted or unsubstituted C 10 to C 60 condensed ring group, substituted or unsubstituted C 6 to C 30 aralkyl, substituted or unsubstituted C 6 to C 30 aryloxy, substituted or unsubstituted C 6 to C 30 arylthio, R 3 and R 4 can be connected to each other to form an aliphatic ring, an aromatic ring, a heteroaromatic ring, a condensed ring or a heterocondensed ring;
    所述R5选自氢、氘、取代或未取代的C1～C10的烷基、取代或未取代的C6～C30的芳基；The R 5 is selected from hydrogen, deuterium, substituted or unsubstituted C 1 to C 10 alkyl, substituted or unsubstituted C 6 to C 30 aryl;
    所述式Ⅱ-1～式Ⅱ-7所示化合物上的任意一个氢可以各自独立地被氘、烷基或环烷基取代。Any hydrogen on the compounds represented by formula II-1 to formula II-7 can be independently replaced by deuterium, alkyl or cycloalkyl.
  4. 根据权利要求1所述的芳香胺化合物，其特征在于，所述Ar2选自取代或未取代的C6～C30的芳基、取代或未取代的C5～C30的杂芳基、取代或未取代的C10～C30的稠环芳基、取代或未取代的C9～C30的杂稠环芳基、取代或未取代的C3～C15的环烷基中的任意一种。The aromatic amine compound according to claim 1, characterized in that Ar2 is selected from any one of a substituted or unsubstituted C6 - C30 aryl group, a substituted or unsubstituted C5 - C30 heteroaryl group, a substituted or unsubstituted C10 - C30 fused ring aryl group, a substituted or unsubstituted C9 - C30 heterofused ring aryl group, and a substituted or unsubstituted C3 - C15 cycloalkyl group.
  5. 根据权利要求1所述的芳香胺化合物，其特征在于，所述Ar2选自下列a-1至a-92所示基团中的任意一种：




    The aromatic amine compound according to claim 1, characterized in that Ar 2 is selected from any one of the following groups represented by a-1 to a-92:




  6. 根据权利要求1所述的芳香胺化合物，其特征在于，所述L2选自单键、 中的任意一种。The aromatic amine compound according to claim 1, characterized in that L2 is selected from a single bond, Any one of .
  7. 根据权利要求1所述的芳香胺化合物，其特征在于，所述式Ⅰ所示化合物选自下述所示化合物中的任意一种：
































    The aromatic amine compound according to claim 1, characterized in that the compound represented by formula I is selected from any one of the following compounds:
































  8. 如权利要求1-7任一所述的芳香胺化合物在有机电致发光领域中的应用。Use of the aromatic amine compound as claimed in any one of claims 1 to 7 in the field of organic electroluminescence.
  9. 一种有机电致发光器件，其特征在于，包括依次设置在衬底基板上的阳极、空穴传输层、发光辅助层、发光层、电子传输区和阴极；其中，所述发光辅助层和/或空穴传输层中包括一种或多种权利要求1-7任一所述的芳香胺化合物。 An organic electroluminescent device, characterized in that it includes an anode, a hole transport layer, a luminescence auxiliary layer, a luminescent layer, an electron transport region and a cathode arranged in sequence on a substrate; wherein the luminescence auxiliary layer and/or the hole transport layer includes one or more aromatic amine compounds described in any one of claims 1 to 7.
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