WO2020244259A1 - 有机化合物及其制备方法、有机发光二极管电致发光器件 - Google Patents

有机化合物及其制备方法、有机发光二极管电致发光器件 Download PDF

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WO2020244259A1
WO2020244259A1 PCT/CN2020/077435 CN2020077435W WO2020244259A1 WO 2020244259 A1 WO2020244259 A1 WO 2020244259A1 CN 2020077435 W CN2020077435 W CN 2020077435W WO 2020244259 A1 WO2020244259 A1 WO 2020244259A1
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organic compound
emitting diode
organic
electroluminescent device
light emitting
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罗佳佳
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武汉华星光电半导体显示技术有限公司
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Priority to US16/753,843 priority Critical patent/US11545638B2/en
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/40—Organosilicon compounds, e.g. TIPS pentacene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/656—Aromatic compounds comprising a hetero atom comprising two or more different heteroatoms per ring
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers

Definitions

  • This application relates to the field of organic electroluminescence technology, in particular to an organic compound and a preparation method thereof, and an organic light emitting diode electroluminescence device.
  • Organic light-emitting diodes do not require a backlight for active light emission, have high luminous efficiency, large viewing angle, fast response speed, large temperature adaptation range, relatively simple production and processing technology, and low driving voltage , Low energy consumption, lighter and thinner, flexible display and other advantages, have huge application prospects, attracting the attention of many researchers.
  • the hole transport material is the thickest layer. There has always been a contradiction between its energy level and hole mobility. Specifically, the highest Occupied Molecular Orbital (HOMO) energy level of hole transport materials with high hole mobility does not match the materials on both sides. The level mismatch will cause the drive voltage of the OLED device to increase.
  • HOMO Occupied Molecular Orbital
  • the purpose of this application is to provide an organic compound, a preparation method thereof, and an organic light-emitting diode electroluminescent device.
  • the organic compound has a suitable HOMO energy level and high hole mobility.
  • Organic light emitting diode electroluminescent devices When applied to an organic light-emitting diode electroluminescent device , Organic light emitting diode electroluminescent devices have high maximum current efficiency, high maximum external quantum efficiency and long service life.
  • the R 1 is a first electron donating group
  • the R 2 is a second electron donating group, H, a phenyl group or an alkyl group
  • the R 3 is H or C(CH 3 ) 3
  • the R 4 is H or C(CH 3 ) 3
  • the X is O or S
  • the first electron-donating group and the second electron-donating group each independently have one of the following structures
  • said R 5 and said R 6 are each independently selected from H, phenyl and alkyl, and said X 1 is selected from empty bond, single bond, O, S, isopropyl and Si(CH 3 ) 2 Any one of the X 2 is selected from any one of an empty bond, a single bond, O, S, isopropyl and Si(CH 3 ) 2 .
  • the first electron-donating group and the second electron-donating group each independently have a structure represented by one of the following formulas,
  • the organic compound has a structure selected from one of the following,
  • both R 3 and R 4 are tert-butyl.
  • the organic compound has a structure selected from one of the following,
  • the X is O.
  • the organic light-emitting diode electroluminescent device includes a hole transport layer, the hole transport layer includes an organic compound, and the organic compound has a structure represented by the following general formula (A) ,
  • the R 1 is a first electron donating group
  • the R 2 is a second electron donating group, H, a phenyl group or an alkyl group
  • the R 3 is H or C(CH 3 ) 3
  • the R 4 is H or C(CH 3 ) 3
  • the X is O or S
  • the first electron-donating group and the second electron-donating group each independently have one of the following structures
  • said R 5 and said R 6 are each independently selected from H, phenyl and alkyl, and said X 1 is selected from empty bond, single bond, O, S, isopropyl and Si(CH 3 ) 2 Any one of the X 2 is selected from any one of an empty bond, a single bond, O, S, isopropyl and Si(CH 3 ) 2 .
  • the first electron donating group and the second electron donating group each independently have a structure represented by one of the following formulas,
  • the organic compound has a structure selected from one of the following,
  • both R 3 and R 4 are tert-butyl.
  • the organic compound has a structure selected from one of the following,
  • the X is O.
  • a method for preparing an organic compound which comprises the following steps:
  • organic compound B organic compound C
  • palladium catalyst tri-tert-butylphosphine tetrafluoroborate and alkali are added to the organic solvent to obtain a mixture;
  • the mixture is reacted at a temperature of 110°C-130°C for 20h-28h, then cooled, extracted, and separated and purified to obtain the organic compound,
  • the R 3 is H or C(CH 3 ) 3
  • the R 4 is H or C(CH 3 ) 3
  • the X is O or S
  • the organic compound C is selected from at least one of the following structures,
  • the R 5 and the R 6 are each independently selected from H, phenyl and alkyl, and the X 1 is selected from the group consisting of empty bonds, single bonds, O, S, isopropyl and Si(CH 3 ) 2 Any one, the X 2 is selected from any one of a void bond, a single bond, O, S, isopropyl and Si(CH 3 ) 2 .
  • the molar ratio of the organic compound B to the organic compound C ranges from 5: (10-13).
  • the organic compound C is selected from at least one of the following structures:
  • the mixture is reacted for 24 hours at a temperature of 120° C., and then cooled, extracted, and separated and purified to obtain the organic compound.
  • the present application provides an organic compound, a preparation method thereof, and an organic light emitting diode electroluminescent device.
  • the organic compound has a suitable HOMO energy level and a high hole mobility.
  • the organic compound when used in the hole transport layer of an organic light emitting diode electroluminescent device, the organic light emitting diode electroluminescent device has a high maximum current efficiency and a high maximum external quantum efficiency And long service life.
  • Fig. 1 is a schematic diagram of the structure of a top-emitting organic light-emitting diode electroluminescent device.
  • R 1 is the first electron donating group
  • R 2 is the second electron donating group
  • H phenyl or alkyl
  • R 3 is H or C(CH 3 ) 3
  • R 4 is H or C(CH 3 ) 3
  • X is O or S
  • the first electron donating group and the second electron donating group each independently have one of the following structures
  • R 5 and R 6 are each independently selected from H, phenyl and alkyl, and X 1 is selected from any one of a void bond, a single bond, O, S, isopropyl and Si(CH 3 ) 2 , X 2 is selected from any one of an empty bond, a single bond, O, S, an isopropyl group, and Si(CH 3 ) 2 .
  • the organic compound of the present application is equipped with specific electron-donating groups on the basis of the structure of spirosilicofluorene as the core, so that the organic compound has a suitable HOMO energy level and LUMO energy level, and has a very high hole transport mobility. .
  • the main reason is that while the spirosilicofluorene has a strong electron-donating ability, the specific electron-donating group R 1 makes the organic compound have high hole mobility, and the selection of the specific electron-donating group R 1 makes the organic The compound has suitable HOMO energy level and LUMO energy level.
  • the organic compound of the present application uses spirosilicofluorene as the core to improve the stability of the organic compound.
  • the organic compound When the organic compound is applied to the organic light-emitting diode electroluminescent device, the organic light-emitting diode electroluminescent device has more advantages. Long service life.
  • the first electron-donating group and the second electron-donating group each independently have a structure represented by one of the following formulas,
  • the organic compound has a structure selected from one of the following,
  • R 3 and R 4 are both tert-butyl, which improves the stability of the organic compound.
  • the organic compound is applied to the organic light-emitting diode electroluminescent device, the use of the organic light-emitting diode electroluminescent device is improved. life.
  • the organic compound has a structure selected from one of the following,
  • X is O.
  • organic compound 1 (3,7-bisdiphenylamine-3',7'-di-tert-butylspiro[dibenzosilole-5,10'diphenyl]) was synthesized according to the following synthetic route:
  • the preparation method of organic compound 1 includes the following steps:
  • the organic compound 2 (3,7-bisdiphenylamine spiro[dibenzosilole-5,10'diphenyl]) was synthesized according to the following synthetic route:
  • the preparation method of organic compound 2 includes the following steps:
  • organic compound 3 (3,7-biscarbazole-3',7'-di-tert-butylspiro[dibenzosilole-5,10'diphenyl]) was synthesized according to the following synthetic route:
  • the preparation method of organic compound 3 includes the following steps:
  • Azole (2.00g, 12mmol), palladium acetate (180mg, 0.8mmol) and tri-tert-butylphosphine tetrafluoroborate (0.68g, 2.4mmol); then add NaOt-Bu (1.16g, 12mmol) in the glove box In an argon atmosphere, inject 100 mL of toluene with dewatering and deoxygenation into a two-neck flask, and react at 120°C for 24 hours; cool to room temperature, pour the reaction solution into 200 mL of ice water, extract three times with dichloromethane, and combine the organic The phase was spun into silica gel and separated and purified by column chromatography (dichloromethane: n-hexane, v: v, 1:4) to obtain 3.0 g of white powder.
  • organic compound 4 (3,7-bis9,9'-dimethylacridine-3',7'-di-tert-butylspiro[dibenzosilole-5,10' was synthesized according to the following synthetic route Diphenyl]):
  • the preparation method of organic compound 4 includes the following steps:
  • Example 1 The organic compound 1, organic compound 2, organic compound 3, and organic compound 4 prepared in Example 1 to Example 4 were tested by mass spectrometry and electrochemical energy level. The test results are shown in Table 1 below.
  • the HOMO energy levels of organic compound 1 and organic compound 2 are similar, mainly because R1 and R2 of substituted spirosilfluorene are the same; the HOMO energy levels of organic compound 1, organic compound 3 and organic compound 4 are quite different, mainly due to the substituents The difference between R1 and R2 is caused.
  • the most suitable range of HOMO energy level for the preparation material of the hole transport layer that matches the traditional hole injection layer material HATCN is -5.60 ⁇ -5.70 eV.
  • the traditional hole transport organic compound 4,4'-bis(N- The HOMO energy level of carbazole) biphenyl (CBP) is -6.0.
  • the traditional hole transport organic compound CBP deviates from the most suitable range by more than 0.3ev.
  • organic compound 1, organic compound 2 and organic compound 4 of this application are all in Within the most suitable range, and the deviation of the organic compound 3 from the optimal range is only 0.004ev. Therefore, the organic compounds 1-4 of this application have suitable HOMO energy levels. In addition, the organic compound of the present application also has a suitable LUMO energy level.
  • the organic compound 1, the organic compound 2, the organic compound 3, the organic compound 4, and the traditional hole transport material CBP are respectively applied to top-emission organic light-emitting diode electroluminescent devices to prepare organic light-emitting diodes.
  • the structure diagram of the top-emission organic light-emitting diode electroluminescent device is shown in Figure 1.
  • the hole blocking layer 6 the electron transport layer 7, the electron injection layer 8, the cathode 9 and the light outcoupling layer 10.
  • Table 2 The composition and thickness of the top-emission organic light-emitting diode electroluminescent device are shown in Table 2.
  • the organic light-emitting diode electroluminescent device 1, the organic light-emitting diode electroluminescent device 2, the organic light-emitting diode electroluminescent device 3, the organic light-emitting diode electroluminescent device 4, and the organic light-emitting diode electroluminescent device 5 are respectively subjected to current-voltage -Brightness test and life test, the test results obtained are shown in Table 3 below.
  • the organic light-emitting diode electroluminescent device 1-4 made from the organic compound 1-4 has high Highest current efficiency, high maximum external quantum efficiency and long service life.
  • the HOMO energy level of the organic compound 3 is -5.56 eV, which makes the performance of the organic light emitting diode electroluminescent device 3 slightly lower than that of the organic light emitting diode electro device 1, the organic light emitting diode electro device 2 and the organic light emitting diode
  • the main reason for the diode electro-induced device 4 is that the material HATCN of the hole injection layer matches the HOMO energy level of the preparation material of the hole transport layer, and the most suitable range is -5.60 to -5.70 eV.
  • organic compound 1 and organic compound 2 are compared to organic light-emitting diode electro-devices.
  • Organic compound 1 is prepared by introducing t-butyl in the central core.
  • the life of the organic light-emitting diode electro-induced device is increased by 36.4%.
  • Organic light-emitting diode electroluminescent devices 1-4 prepared by organic compounds 1-4 have high maximum current efficiency and high maximum external quantum efficiency, indicating that the energy levels and hole transport properties of organic compounds 1-4 are comparable to those of organic light-emitting diodes.
  • the other film layers in the electroluminescence device are matched, and the carrier recombination efficiency is high.

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Abstract

本申请提供一种有机化合物及其制备方法、有机发光二极管电致发光器件，该有机化合物具有合适的HOMO能级以及高的空穴迁移率。与传统的空穴传输材料相比，该有机化合物应用于有机发光二极管电致发光器件的空穴传输层中时，有机发光二极管电致发光器件具有高的最高电流效率、高的最大外量子效率以及长的使用寿命。

Description

有机化合物及其制备方法、有机发光二极管电致发光器件 技术领域
本申请涉及有机电致发光技术领域，尤其涉及一种有机化合物及其制备方法、有机发光二极管电致发光器件。
背景技术
有机电致发光二极管(organic light-emitting diodes，OLEDs)以其主动发光不需要背光源、发光效率高、可视角度大、响应速度快、温度适应范围大、生产加工工艺相对简单、驱动电压低、能耗小、更轻更薄以及柔性显示等优点而具有巨大的应用前景，吸引了众多研究者的关注。
对于目前使用的顶发射OLED器件，空穴传输材料作为最厚的一层。其能级以及空穴迁移率一直存在矛盾的关系，具体为空穴迁移率高的空穴传输材料的最高占据分子轨道(Highest Occupied Molecular Orbital，HOMO)能级与其两侧的材料不匹配，能级不匹配会导致OLED器件的驱动电压升高。
因此，有必要提供一种高迁移率且能级匹配的空穴传输化合物。
技术问题
本申请的目的在于提供一种有机化合物及其制备方法、有机发光二极管电致发光器件，该有机化合物具有合适的HOMO能级以及高的空穴迁移率，应用于有机发光二极管电致发光器件时，有机发光二极管电致发光器件具有高的最高电流效率、高的最大外量子效率以及长的使用寿命。
技术解决方案
一种有机化合物，所述有机化合物具有如下通式(A)所示的结构，
Figure PCTCN2020077435-appb-000001
其中，所述R 1为第一给电子基团，所述R 2为第二给电子基团、H、苯基或烷基，所述R 3为H或C(CH 3) 3，所述R 4为H或C(CH 3) 3，所述X为O或S，所述第一给电子基团和所述第二给电子基团各自独立地具有如下之一的结构，
Figure PCTCN2020077435-appb-000002
其中，所述R 5和所述R 6各自独立地选自H、苯基以及烷基，所述X 1选自空键、单键、O、S、异丙基以及Si(CH 3) 2中的任意一种，所述X 2选自空键、单键、O、S、异丙基以及Si(CH 3) 2中的任意一种。
在上述有机化合物中，所述第一给电子基团和所述第二给电子基团各自独立地具有如下式之一所示的结构，
Figure PCTCN2020077435-appb-000003
在上述有机化合物中，所述有机化合物具有选自如下之一所示的结构，
Figure PCTCN2020077435-appb-000004
Figure PCTCN2020077435-appb-000005
在上述有机化合物中，所述R 3和R 4均为叔丁基。
在上述有机化合物中，所述有机化合物具有选自如下之一所示的结构，
Figure PCTCN2020077435-appb-000006
在上述有机化合物中，所述X为O。
一种有机发光二极管电致发光器件，所述有机发光二极管电致发光器件包括空穴传输层，所述空穴传输层包括有机化合物，所述有机化合物具有如下通式(A)所示的结构，
Figure PCTCN2020077435-appb-000007
其中，所述R 1为第一给电子基团，所述R 2为第二给电子基团、H、苯基或烷基，所述R 3为H或C(CH 3) 3，所述R 4为H或C(CH 3) 3，所述X为O或S，所述第一给电子基团和所述第二给电子基团各自独立地具有如下之一的结构，
Figure PCTCN2020077435-appb-000008
其中，所述R 5和所述R 6各自独立地选自H、苯基以及烷基，所述X 1选自空键、单键、O、S、异丙基以及Si(CH 3) 2中的任意一种，所述X 2选自空键、单键、O、S、异丙基以及Si(CH 3) 2中的任意一种。
在上述有机发光二极管电致发光器件中，所述第一给电子基团和所述第二给电子基团各自独立地具有如下式之一所示的结构，
Figure PCTCN2020077435-appb-000009
在上述有机发光二极管电致发光器件中，所述有机化合物具有选自如下之一所示的结构，
Figure PCTCN2020077435-appb-000010
在上述有机发光二极管电致发光器件中，所述R 3和R 4均为叔丁基。
在上述有机发光二极管电致发光器件中，所述有机化合物具有选自如下之一所示的结构，
Figure PCTCN2020077435-appb-000011
在上述有机发光二极管电致发光器件中，所述X为O。
一种有机化合物的制备方法，所述有机化合物的制备方法包括如下步骤：
在无水无氧条件下，将有机化合物B、有机化合物C、钯催化剂、三叔丁基膦四氟硼酸盐以及碱加入至有机溶剂中，得混合物；
所述混合物在温度为110℃-130℃的条件下反应20h-28h后，经冷却、萃取以及分离纯化，得所述有机化合物，
其中，所述有机化合物B的结构如下，
Figure PCTCN2020077435-appb-000012
所述R 3为H或C(CH 3) 3，所述R 4为H或C(CH 3) 3，所述X为O或S，
所述有机化合物C选自如下所示结构中的至少一种，
Figure PCTCN2020077435-appb-000013
所述R 5和所述R 6各自独立地选自H、苯基以及烷基，所述X 1选自空键、单键、O、S、异丙基以及Si(CH 3) 2中的任意一种，所述X 2选自空键、单键、O、S、异丙基以及Si(CH 3) 2中的任意一种。
在上述制备方法中，所述有机化合物B与所述有机化合物C的摩尔比的取值范围为5：(10-13)。
在上述制备方法中，所述有机化合物C选自如下结构中的至少一种：
Figure PCTCN2020077435-appb-000014
在上述制备方法中，所述混合物在温度为120℃的条件下反应24h后，经冷却、萃取以及分离纯化，得所述有机化合物。
有益效果
本申请提供一种有机化合物及其制备方法、有机发光二极管电致发光器件，该有机化合物具有合适的HOMO能级以及高的空穴迁移率。与传统的空穴传输材料相比，该有机化合物应用于有机发光二极管电致发光器件的空穴传输层中时，有机发光二极管电致发光器件具有高的最高电流效率、高的最大外量子效率以及长的使用寿命。
附图说明
图1为顶发光型有机发光二极管电致发光器件的结构示意图。
本发明的实施方式
下面将结合本申请实施例中的附图，对本申请实施例中的技术方案进行清楚、完整地描述。显然，所描述的实施例仅仅是本申请一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本申请保护的范围。
一种有机化合物，有机化合物具有如下通式(A)所示的结构，
Figure PCTCN2020077435-appb-000015
其中，R 1为第一给电子基团，R 2为第二给电子基团、H、苯基或烷基，R 3为H或C(CH 3) 3，R 4为H或C(CH 3) 3，X为O或S，第一给电子基团和第二给电子基团各自独立地具有如下之一的结构，
Figure PCTCN2020077435-appb-000016
其中，R 5和R 6各自独立地选自H、苯基以及烷基，X 1选自空键、单键、O、S、异丙基以及Si(CH 3) 2中的任意一种，X 2选自空键、单键、O、S、异丙基以及Si(CH 3) 2中的任意一种。
本申请的有机化合物在螺硅芴为核的结构基础上，配上特定的给 电子基团，使得有机化合物具有合适的HOMO能级以及LUMO能级的同时，具有非常高的空穴传输迁移率。主要原因在于，螺硅芴具有强的给电子能力的同时，配合特定的给电子基团R 1使得有机化合物具有高的空穴迁移率，且通过特定的给电子基团R 1的选择使得有机化合物具有合适的HOMO能级以及LUMO能级。此外，相对于以螺芴为核，本申请的有机化合物以螺硅芴为核能提高有机化合物的稳定性，有机化合物应用于有机发光二极管电致发光器件时，有机发光二极管电致发光器件具有更长的使用寿命。
在一些实施例中，第一给电子基团和第二给电子基团各自独立地具有如下式之一所示的结构，
Figure PCTCN2020077435-appb-000017
在一些实施例中，有机化合物具有选自如下之一所示的结构，
Figure PCTCN2020077435-appb-000018
在一些实施例中，R 3和R 4均为叔丁基，使得有机化合物的稳定性提高，该有机化合物应用于有机发光二极管电致发光器件时，从而提高有机发光二极管电致发光器件的使用寿命。
在一些实施例中，有机化合物具有选自如下之一所示的结构，
Figure PCTCN2020077435-appb-000019
在一些实施例中，X为O。
以下结合具体实施例对上述技术方案进行描述。
实施例一
本实施例根据如下合成路线合成有机化合物1(3,7-双二苯胺-3',7'-二叔丁基螺[二苯并噻咯-5,10'二苯])：
Figure PCTCN2020077435-appb-000020
其中，有机化合物1的制备方法包括如下步骤：
向250mL二口瓶中加入原料1(3,7-二溴-3',7'-二叔丁基螺[二苯并噻咯-5,10'二苯]，3.08g，5mmol)、二苯胺(2.02g，12mmol)、醋酸钯(180mg，0.8mmol)和三叔丁基膦四氟硼酸盐(0.68g，2.4mmol)；然后在手套箱中加入NaOt-Bu(1.16g，12mmol)，在氩气氛围下向二口 瓶中注入100mL除水除氧的甲苯，在120℃反应24小时后；冷却至室温，将反应液倒入200mL冰水中，经过二氯甲烷萃取三次，合并有机相，旋成硅胶，柱层析(二氯甲烷:正己烷，v:v，1:4)分离纯化，得白色粉末3.1g。
实施例二
本实施例根据如下合成路线合成有机化合物2(3,7-双二苯胺螺[二苯并噻咯-5,10'二苯])：
Figure PCTCN2020077435-appb-000021
其中，有机化合物2的制备方法包括如下步骤：
向250mL二口瓶中加入原料2(3,7-二溴螺[二苯并噻咯-5,10'二苯]，2.52g，5mmol)、二苯胺(2.02g，12mmol)、醋酸钯(180mg，0.8mmol)和三叔丁基膦四氟硼酸盐(0.68g，2.4mmol)，然后在手套箱中加入NaOt-Bu(1.16g，12mmol)，在氩气氛围下向二口瓶中注入100mL除水除氧的甲苯，在120℃反应24小时后；冷却至室温，将反应液倒入200mL冰水中，二氯甲烷萃取三次，合并有机相，旋成硅胶，柱层析(二氯甲烷:正己烷，v:v，1:4)分离纯化，得白色粉末2.8g。
实施例三
本实施例根据如下合成路线合成有机化合物3(3,7-双咔唑-3',7'- 二叔丁基螺[二苯并噻咯-5,10'二苯])：
Figure PCTCN2020077435-appb-000022
其中，有机化合物3的制备方法包括如下步骤：
向250mL二口瓶中加入原料1(3,7-二溴-3',7'-二叔丁基螺[二苯并噻咯-5,10'二苯]，3.08g，5mmol)、咔唑(2.00g，12mmol)、醋酸钯(180mg，0.8mmol)和三叔丁基膦四氟硼酸盐(0.68g，2.4mmol)；然后在手套箱中加入NaOt-Bu(1.16g，12mmol)，在氩气氛围下向二口瓶中注入100mL除水除氧的甲苯，在120℃反应24小时后；冷却至室温，将反应液倒入200mL冰水中，经过二氯甲烷萃取三次，合并有机相，旋成硅胶，柱层析(二氯甲烷:正己烷，v:v，1:4)分离纯化，得白色粉末3.0g。
实施例四
本实施例根据如下合成路线合成有机化合物4(3,7-双9,9’-二甲基吖啶-3',7'-二叔丁基螺[二苯并噻咯-5,10'二苯])：
Figure PCTCN2020077435-appb-000023
其中，有机化合物4的制备方法包括如下步骤：
向250mL二口瓶中加入原料1(3,7-二溴-3',7'-二叔丁基螺[二苯并噻 咯-5,10'二苯]，3.08g，5mmol)、9,9’-二甲基吖啶(2.50g，12mmol)、醋酸钯(180mg，0.8mmol)和三叔丁基膦四氟硼酸盐(0.68g，2.4mmol)；然后在手套箱中加入NaOt-Bu(1.16g，12mmol)，在氩气氛围下向二口瓶中注入100mL除水除氧的甲苯，在120℃反应24小时后；冷却至室温，将反应液倒入200mL冰水中，经过二氯甲烷萃取三次，合并有机相，旋成硅胶，柱层析(二氯甲烷:正己烷，v:v，1:4)分离纯化，得白色粉末3.4g。
实施例五
对实施例一至实施例四制备的有机化合物1、有机化合物2、有机化合物3以及有机化合物4进行质谱以及电化学能级的测试，测试结果如下表1所示。
表1有机化合物1-4的质谱和电化学能级测试结果
Figure PCTCN2020077435-appb-000024
由表1可知，有机化合物1、有机化合物2、有机化合物3以及有机化合物4经过质谱分析的分子量与它们各自的标准质量吻合，即有机化合物1、有机化合物2、有机化合物3以及有机化合物4均为 设计的目标产物。另外，有机化合物1、有机化合物2、有机化合物3以及有机化合物4的LUMO能级都为-2.69eV，主要原因在于LUMO能级由有机化合物1-4的中心核决定，有机化合物1-4的中心核都是一样，即均为螺硅芴。有机化合物1和有机化合物2的HOMO能级接近，主要原因在取代螺硅芴的R1和R2相同；有机化合物1、有机化合物3以及有机化合物4的HOMO能级差异较大，主要是由于取代基R1和取代基R2的不同造成的。与传统空穴注入层的材料HATCN匹配的空穴传输层的制备材料的HOMO能级最合适的范围是-5.60～-5.70eV，传统的空穴传输有机化合物4,4’-二(N-咔唑)联苯(CBP)的HOMO能级为-6.0，传统的空穴传输有机化合物CBP偏离最合适的范围超过0.3ev，而本申请的有机化合物1、有机化合物2以及有机化合物4均在最合适的范围内，且有机化合物3偏离最佳范围仅为0.004ev。故，本申请有机化合物1-4具有合适的HOMO能级。此外，本申请的有机化合物也具有合适的LUMO能级。
实施例六
本实施例将有机化合物1、有机化合物2、有机化合物3、有机化合物4以及传统的空穴传输材料CBP分别应用于顶发光型有机发光二极管电致发光器件中，以分别制备得到有机发光二极管电致发光器件1、有机发光二极管电致发光器件2、有机发光二极管电致发光器件3、有机发光二极管电致发光器件4以及有机发光二极管电致发光器件5。顶发光型有机发光二极管电致发光器件的结构示意图如图 1所示，从下至上依次包括阳极1、空穴注入层2、空穴传输层3、电子阻挡层4、有机发光层5、空穴阻挡层6、电子传输层7、电子注入层8、阴极9以及光耦合输出层10。顶发光型有机发光二极管电致发光器件组成以及厚度如下表2。
表2顶发光型有机发光二极管电致发光器件组成以及厚度
Figure PCTCN2020077435-appb-000025
Figure PCTCN2020077435-appb-000026
对有机发光二极管电致发光器件1、有机发光二极管电致发光器件2、有机发光二极管电致发光器件3、有机发光二极管电致发光器件4以及有机发光二极管电致发光器件5分别进行电流-电压-亮度测试和寿命测试，得到测试结果如下表3所示。
表3有机发光二极管电致发光器件1-5的电流-电压-亮度测试和寿命测试结果
Figure PCTCN2020077435-appb-000027
Figure PCTCN2020077435-appb-000028
由上表3可知，与传统的空穴传输材料CBP制得的有机发光二极管电致发光器件5相比，由有机化合物1-4制备的有机发光二极管电致发光器件1-4都具有高的最高电流效率、高的最大外量子效率以及长的使用寿命。其中，有机化合物3的HOMO能级为-5.56eV，使得其制得的有机发光二极管电致发光器件3的性能略低于有机发光二极管电致器件1、有机发光二极管电致器件2以及有机发光二极管电致器件4，主要原因在于空穴注入层的材料HATCN匹配空穴传输层的制备材料的HOMO能级最合适的范围是-5.60～-5.70eV。此外，在有机发光二极管电致器件的使用寿命方面，有机化合物1和有机化合物2制得有机发光二极管电致器件相比，有机化合物1由于在中心核引入叔丁基之后，有机化合物1制备得到的有机发光二极管电致器件的寿命提升36.4％。有机化合物1-4制备的有机发光二极管电致发光器件1-4具有高的最高电流效率以及高的最大外量子效率，表明有机化合物1-4的能级以及空穴传输性能与有机发光二极管电致发光器中的其他膜层匹配，载流子复合效率高。
以上实施例的说明只是用于帮助理解本申请的技术方案及其核心思想；本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本申请各 实施例的技术方案的范围。

Claims (16)

  1. 一种有机化合物，其中，所述有机化合物具有如下通式(A)所示的结构，
    Figure PCTCN2020077435-appb-100001
    其中，所述R 1为第一给电子基团，所述R 2为第二给电子基团、H、苯基或烷基，所述R 3为H或C(CH 3) 3，所述R 4为H或C(CH 3) 3，所述X为O或S，所述第一给电子基团和所述第二给电子基团各自独立地具有如下之一的结构，
    Figure PCTCN2020077435-appb-100002
    其中，所述R 5和所述R 6各自独立地选自H、苯基以及烷基，所述X 1选自空键、单键、O、S、异丙基以及Si(CH 3) 2中的任意一种，所述X 2选自空键、单键、O、S、异丙基以及Si(CH 3) 2中的任意一种。
  2. 根据权利要求1所述的有机化合物，其中，所述第一给电子基团和所述第二给电子基团各自独立地具有如下式之一所示的结构，
    Figure PCTCN2020077435-appb-100003
  3. 根据权利要求1所述的有机化合物，其中，所述有机化合物具有选自如下之一所示的结构，
    Figure PCTCN2020077435-appb-100004
    Figure PCTCN2020077435-appb-100005
  4. 根据权利要求1所述的有机化合物，其中，所述R 3和R 4均为叔丁基。
  5. 根据权利要求1所述的有机化合物，其中，所述有机化合物具有选自如下之一所示的结构，
    Figure PCTCN2020077435-appb-100006
  6. 根据权利要求1所述的有机化合物，其中，所述X为O。
  7. 一种有机发光二极管电致发光器件，其中，所述有机发光二极管电致发光器件包括空穴传输层，所述空穴传输层包括有机化合物，所述有机化合物具有如下通式(A)所示的结构，
    Figure PCTCN2020077435-appb-100007
    其中，所述R 1为第一给电子基团，所述R 2为第二给电子基团、H、苯基或烷基，所述R 3为H或C(CH 3) 3，所述R 4为H或C(CH 3) 3，所述X为O或S，所述第一给电子基团和所述第二给电子基团各自独立地具有如下之一的结构，
    Figure PCTCN2020077435-appb-100008
    其中，所述R 5和所述R 6各自独立地选自H、苯基以及烷基，所述X 1选自空键、单键、O、S、异丙基以及Si(CH 3) 2中的任意一种，所述X 2选自空键、单键、O、S、异丙基以及Si(CH 3) 2中的任意一种。
  8. 根据权利要求7所述的有机发光二极管电致发光器件，其中，所述第一给电子基团和所述第二给电子基团各自独立地具有如下式之一所示的结构，
    Figure PCTCN2020077435-appb-100009
  9. 根据权利要求7所述的有机发光二极管电致发光器件，其中，
    所述有机化合物具有选自如下之一所示的结构，
    Figure PCTCN2020077435-appb-100010
  10. 根据权利要求7所述的有机发光二极管电致发光器件，其中，所述R 3和R 4均为叔丁基。
  11. 根据权利要求7所述的有机发光二极管电致发光器件，其中，所述有机化合物具有选自如下之一所示的结构，
    Figure PCTCN2020077435-appb-100011
  12. 根据权利要求7所述的有机发光二极管电致发光器件，其中，所述X为O。
  13. 一种有机化合物的制备方法，其中，所述有机化合物的制备方法包括如下步骤：
    在无水无氧条件下，将有机化合物B、有机化合物C、钯催化剂、三叔丁基膦四氟硼酸盐以及碱加入至有机溶剂中，得混合物；
    所述混合物在温度为110℃-130℃的条件下反应20h-28h后，经冷却、萃取以及分离纯化，得所述有机化合物，
    其中，所述有机化合物B的结构如下，
    Figure PCTCN2020077435-appb-100012
    所述R 3为H或C(CH 3) 3，所述R 4为H或C(CH 3) 3，所述X为O或S，
    所述有机化合物C选自如下所示结构中的至少一种，
    Figure PCTCN2020077435-appb-100013
    所述R 5和所述R 6各自独立地选自H、苯基以及烷基，所述X 1选自空键、单键、O、S、异丙基以及Si(CH 3) 2中的任意一种，所述X 2选自空键、单键、O、S、异丙基以及Si(CH 3) 2中的任意一种。
  14. 根据权利要求13所述的有机化合物的制备方法，其中，所述有机化合物B与所述有机化合物C的摩尔比的取值范围为5：(10-13)。
  15. 根据权利要求13所述的有机化合物的制备方法，其中，所述有机化合物C选自如下结构中的至少一种：
    Figure PCTCN2020077435-appb-100014
  16. 根据权利要求13所述的所述的有机化合物的制备方法，其中，所述混合物在温度为120℃的条件下反应24h后，经冷却、萃取以及分离纯化，得所述有机化合物。
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