WO2020232852A1 - 有机发光材料及其制备方法、有机发光器件 - Google Patents

有机发光材料及其制备方法、有机发光器件 Download PDF

Info

Publication number
WO2020232852A1
WO2020232852A1 PCT/CN2019/101491 CN2019101491W WO2020232852A1 WO 2020232852 A1 WO2020232852 A1 WO 2020232852A1 CN 2019101491 W CN2019101491 W CN 2019101491W WO 2020232852 A1 WO2020232852 A1 WO 2020232852A1
Authority
WO
WIPO (PCT)
Prior art keywords
triphenylene
organic light
solution
emitting material
reaction liquid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2019/101491
Other languages
English (en)
French (fr)
Inventor
汪亚民
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wuhan China Star Optoelectronics Semiconductor Display Technology Co Ltd
Original Assignee
Wuhan China Star Optoelectronics Semiconductor Display Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wuhan China Star Optoelectronics Semiconductor Display Technology Co Ltd filed Critical Wuhan China Star Optoelectronics Semiconductor Display Technology Co Ltd
Priority to US16/607,647 priority Critical patent/US11254687B2/en
Publication of WO2020232852A1 publication Critical patent/WO2020232852A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/30—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D263/32—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
    • C09K11/06—Luminescent materials, e.g. electroluminescent or chemiluminescent containing organic luminescent materials
    • 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
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1011—Condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/30—Highest occupied molecular orbital [HOMO], lowest unoccupied molecular orbital [LUMO] or Fermi energy values
    • 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]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers

Definitions

  • the invention relates to the field of display technology, in particular to an organic light-emitting material, a preparation method thereof, and an organic light-emitting device.
  • organic light-emitting materials have achieved world-renowned achievements, and many domestic companies have realized the successful lighting of flexible OLED display screens, and various flexible screens have appeared.
  • the present invention provides an organic light-emitting material, a preparation method thereof, and an organic light-emitting device.
  • the organic light-emitting material has a triphenylene derivative with a large ⁇ -conjugated system to improve luminous efficiency.
  • the present invention provides an organic light-emitting material, including a triphenylene derivative, which has a large ⁇ -conjugated system.
  • the molecular structure of one of the triphenylene derivatives is
  • the present invention also provides a preparation method for preparing the organic luminescent material, including the following steps: providing triphenylene boric acid derivatives and dioxazole bromide; adding boric acid to the round bottom flask under the protection of nitrogen , Triphenanthrene boronic acid derivative, dioxazole bromide, potassium carbonate, N,N-dimethylformamide solvent, continue to stir for 1-3 hours to obtain the first mixed liquid; change the temperature of the first mixed liquid Increase the temperature to 40°C-70°C, add tetrakistriphenylphosphonium palladium to the first mixed solution, continue to increase the temperature to 80°C-100°C, and react for 24 hours to 96 hours to obtain the first reaction solution; The first reaction solution is cooled to room temperature, filtered with suction and dried to obtain the organic light-emitting material.
  • the step of providing the triphenylene boronic acid derivative includes dissolving the triphenylene compound in dichloromethane, stirring constantly, and adding anhydrous hydrogen bromide in dichloromethane solution at room temperature, React for 3-12 hours to obtain a second reaction liquid; add anhydrous sodium sulfate to the second reaction liquid, stir well and then stand still to obtain a third reaction liquid; extract the third reaction liquid with dichloromethane Then, the white solid was precipitated with ethanol and dried to obtain the triphenylene derivative intermediate; the triphenylene derivative intermediate was fully dissolved in the tetrahydrofuran solution to obtain the fourth reaction liquid, and the temperature was lowered to keep the temperature at- 70°C to -90°C, and the catalyst butyl lithium was added dropwise until the fourth reaction solution was yellow and reacted for 2-3 hours; and trimethyl borate was added dropwise to the fourth reaction solution until the first The fourth reaction solution is clarified and reacted for 1-3 hours to obtain a fifth
  • the triphenylene compound includes at least one of 1,2-triphenylene, 2,3,6,7-triphenylene, 9.10-triphenylene, and dodecahydrotriphenylene One kind.
  • the molecular structural formula of the triphenylene derivative intermediate is:
  • the step of providing dioxazole bromide includes providing isothiocyanato aryl compounds and keto azide compounds; under the protection of argon, the isothiocyanato aryl compounds are sequentially added to the flask Take the tetrahydrofuran solution and add copper powder to obtain a second mixed solution; heat the second mixed solution to 40°C until the second mixed solution is blue; dissolve the keto azide compound in the tetrahydrofuran solution to prepare To form a ketone azide compound solution; add the ketone azide compound solution dropwise to the second mixed solution, and react at a constant temperature for 6-10 hours until the solution is dark brown; suction filtration and drying to obtain the dioxazole bromide Chemical.
  • the molecular structural formula of the isothiocyanoaryl compound is:
  • the molecular structural formula of the keto azide compound is:
  • the molecular structural formula of the dioxazole bromide is:
  • the present invention also provides an organic light emitting device, including the organic light emitting material.
  • the organic light emitting device includes a first electrode; a hole injection layer provided on the first electrode; a hole transport layer provided on the hole injection layer; a light emitting layer , Arranged on the hole transport layer, the light emitting layer has the organic light emitting material; an electron transport layer, arranged on the light emitting layer; an electron injection layer, arranged on the electron transport layer; second The electrode is arranged on the electron injection layer.
  • the organic light-emitting material, the preparation method thereof, and the organic light-emitting device of the present invention obtain the organic light-emitting material with triphenylene derivatives through the preparation method of Suzuki reaction, that is, it has good planarity and strong visible ⁇ - ⁇ * absorption capacity At the same time, it has the ability of blue fluorescence emission with high quantum yield. Therefore, the triphenylene derivative with large ⁇ -conjugated system has high-efficiency electron transport characteristics. As an efficient electron withdrawing group, it will increase the efficiency of charge transfer and is effective The luminous efficiency of the organic light-emitting device is improved.
  • Fig. 1 is a waveform diagram of the organic light-emitting material of the present invention measured by cyclic voltammetry.
  • Fig. 2 is a fluorescence spectrum diagram of the organic light-emitting material of the present invention in a tetrahydrofuran solution.
  • Fig. 3 is a structural diagram of an organic light emitting device according to an embodiment of the present invention.
  • the organic light-emitting material of the present invention includes triphenylene derivatives, and the molecular structure of one of the triphenylene derivatives is:
  • triphenanthrene derivative structure has a large ⁇ -conjugated system, that is, it has good planarity and strong visible ⁇ - ⁇ * absorption capacity, as well as blue fluorescence emission ability with high quantum yield, so , Triphenanthrene derivatives with large ⁇ -conjugated systems have high-efficiency electron transport properties. As an efficient electron-withdrawing group, it will increase the charge transfer efficiency and improve its luminous efficiency.
  • the present invention also provides a preparation method for preparing the organic light-emitting material with triphenylene derivatives, including the following steps.
  • triphenylene boronic acid derivatives and dioxazole bromide.
  • the step of providing the triphenylene boronic acid derivative includes dissolving the triphenylene compound in dichloromethane, and the triphenylene compound includes 1,2-triphenylene, 2,3,6,7-triphenylene, 9.10-At least one of triphenylene and dodecahydrotriphenylene.
  • 1,2-triphenanthrene is selected as an example to illustrate the preparation method of the present invention in detail. Firstly, it is necessary to form a 1,2-triphenanthrene derivative intermediate, and then form a 1,2-triphenylene boronic acid derivative through the 1,2-triphenylene derivative intermediate to synthesize the 1,2-triphenanthrene derivative
  • the reaction formula of boric acid derivatives is as follows:
  • the 1,2-triphenanthrene derivative intermediate is fully dissolved in the tetrahydrofuran solution to obtain the fourth reaction liquid, and the temperature is lowered to keep the temperature at -70°C to -90°C, and the catalyst butyllithium was added dropwise until the fourth reaction solution was yellow and reacted for 2-3 hours; and trimethyl borate was added dropwise to the fourth reaction solution until the The fourth reaction liquid is clarified and reacted for 1-3 hours to obtain the fifth reaction liquid; add dilute hydrochloric acid to the fifth reaction liquid and stir to precipitate a white solid, which is suction filtered and dried to obtain the triphenylene boronic acid derivative.
  • 1,2-triphenanthrene boronic acid derivatives 1,2-triphenanthrene boronic acid derivatives.
  • the step of providing the bisoxazole bromide includes providing an aryl isothiocyanate compound and a keto azide compound; in this embodiment, the molecular structural formula of the aryl isothiocyanate compound is:
  • the molecular structural formula of the keto azide compound is:
  • the molecular structural formula of the dioxazole bromide is:
  • the isothiocyanato aryl compound and the tetrahydrofuran solution were sequentially added to the flask, and copper powder was added to obtain a second mixed solution; the second mixed solution was heated to 40°C until the second The mixed solution is blue; the keto azide compound is dissolved in the tetrahydrofuran solution to prepare a keto azide compound solution; the keto azide compound solution is added dropwise to the second mixed solution, and the reaction is constant temperature 6-10 Hours, until the solution is dark brown; suction filtration and drying to obtain the dioxazole bromide.
  • the molar ratio of the isothiocyanato aryl compound and the keto azide compound is 1:1.
  • the organic light-emitting material with triphenylene derivative is prepared by Suzuki reaction.
  • the reaction formula of the organic light-emitting material with triphenylene derivatives is as follows:
  • the performance of the organic light-emitting material with triphenylene derivatives is analyzed: firstly, according to the molecules of the organic light-emitting material with triphenylene derivatives Functional analysis and energy level calculation of the structural formula show that the highest occupied orbit (HOMO) energy level is 4.76 eV and the lowest occupied orbit (LUMO) energy level is 1.87 eV, and the energy level difference is 2.89 eV.
  • the highest occupied orbital (HOMO) energy level of 4.76 is lower than that of indium tin oxide (the work function of the conductive substrate of indium tin oxide is 5.3).
  • the organic light-emitting material with the triphenylene derivative is theoretically in line with the organic light-emitting device According to the requirements of the work function of the host material of the light-emitting layer, the energy level difference between oxadiazole and benzodioxazole can effectively increase the luminous efficiency and luminous ability of the device.
  • the organic light-emitting material with triphenylene derivatives is configured into a 0.1 mol/L electrolyte solution, and then 1 ⁇ 10 -6 mol/L tetrahydrofuran and the organic light-emitting material with triphenylene derivatives are prepared
  • the electrode scanning cycle of 100mV/s is performed 10 times to obtain the waveform of cyclic voltammetry.
  • EHOMO e(
  • ELUMO EHOMO-
  • Organic light-emitting materials can be used as materials for light-emitting layers in organic light-emitting devices.
  • the present invention also provides an organic light-emitting device 1, comprising the organic light-emitting material having the triphenylene derivative.
  • the organic light emitting device includes a first electrode 11, a hole injection layer 12, a hole transport layer 13, a light emitting layer 14, an electron transport layer 15, an electron injection layer 16, and a second electrode 17.
  • the hole injection layer 12 is provided on the first electrode 11; the hole transport layer 13 is provided on the hole injection layer 12; the light emitting layer 14 is provided on the hole transport layer 13, the light-emitting layer 14 includes the organic light-emitting material with triphenylene derivatives; the electron transport layer 15 is provided on the light-emitting layer 14; the electron injection layer 16 is provided on the electron transport Layer 15; the second electrode 17 is provided on the electron injection layer 16.
  • the first electrode 11 is an anode, and the second electrode 17 is a cathode.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

本发明公开了一种有机发光材料及其制备方法、有机发光器件，所述有机发光材料具有苯并菲衍生物，其具有良好的平面性和强烈的可见π-π *吸收能力，同时具有高量子产率的荧光发射能力，因此，具有大π共轭体系的苯并菲衍生物具有高效电子传输特性，其作为一种高效的吸电子基团会增加电荷迁移效率，有效提高了有机发光器件的发光效率。

Description

有机发光材料及其制备方法、有机发光器件 技术领域
本发明涉及显示技术领域，具体为一种有机发光材料及其制备方法、有机发光器件。
背景技术
目前，有机发光材料已经取得了举世瞩目的成绩，已经有很多国内公司实现了柔性OLED显示屏幕的成功点亮，出现了各种各样的柔性屏幕。但目前柔性OLED显示屏幕的发光材料不管是成本，还是有机发光器件的稳定性，抑或是发光材料的发光效率的持久性还存在一些问题，因此，丰富和发展有机发光器件中的发光层主体材料是很重要的一件事，进一步研发出具有长寿命和高效率以及性能稳定性的发光层主体材料仍然是研究者们的重要目标。
技术问题
为解决上述技术问题：本发明提供一种有机发光材料及其制备方法、有机发光器件，有机发光材料具有苯并菲衍生物，其具有大π共轭体系，以改善发光效率。
技术解决方案
解决上述问题的技术方案是：本发明提供一种有机发光材料，包括苯并菲衍生物，其具有大π共轭体系。
在本发明一实施例中，其中一种苯并菲衍生物的分子结构式为
Figure PCTCN2019101491-appb-000001
本发明还提供了一种制备方法，用以制作所述的有机发光材料，包括以下步骤：提供苯并菲硼酸衍生物、二恶唑溴化物；在氮气保护下，向圆底烧瓶中加入硼酸、苯并菲硼酸衍生物、二恶唑溴化物、碳酸钾、N,N-二甲基甲酰胺溶剂，持续搅拌1-3小时，得到第一混合液；将所述第一混合液的温度升高至40℃-70℃，向所述第一混合液中加入四三苯基磷钯，继续升高温度至80℃-100℃，反应24小时至96小时，得到第一反应液；将所述第一反应液冷却至室温，抽滤并干燥得到所述有机发光材料。
在本发明一实施例中，在提供苯并菲硼酸衍生物步骤中包括将苯并菲化合物溶解于二氯甲烷中，不断搅拌，并在室温下加入无水溴化氢的二氯甲烷溶液，反应3-12小时，得到第二反应液；向所述第二反应液中加入无水硫酸钠，并充分搅拌后静置，得到第三反应液；用二氯甲烷萃取所述第三反应液，之后用乙醇析出白色固体并烘干，得到苯并菲衍生物中间体；将所述苯并菲衍生物中间体充分溶解于四氢呋喃溶液中，得到第四反应液，降温，使温度保持在-70℃至-90℃，并滴加催化剂丁基锂，直至所述第四反应液呈黄色，反应2-3小时； 向所述第四反应液中滴加硼酸三甲酯，直至所述第四反应液澄清，再反应1-3小时，得到第五反应液；向所述第五反应液中加入稀盐酸，并搅拌，析出白色固体，抽滤烘干得到苯并菲硼酸衍生物。
在本发明一实施例中，所述苯并菲化合物包括1,2-苯并菲、2,3,6,7-苯并菲、9.10-苯并菲、十二氢苯并菲中的至少一种。
在本发明一实施例中，当所述苯并菲化合物为1,2-苯并菲时，所述苯并菲衍生物中间体的分子结构式为：
Figure PCTCN2019101491-appb-000002
所述苯并菲硼酸衍生物的分子结构式为：
Figure PCTCN2019101491-appb-000003
在本发明一实施例中，在提供二恶唑溴化物步骤中包括提供异硫氰芳基化合物、酮基叠氮化合物；在氩气的保护下，向烧瓶中依次加入异硫氰芳基化合物以四氢呋喃溶液，并加入铜粉，得到第二混合液； 加热所述第二混合液至40℃，直至所述第二混合液呈蓝色；将酮基叠氮化合物溶于四氢呋喃溶液中，配制成酮基叠氮化合物溶液；将酮基叠氮化合物溶液滴加至所述第二混合液中，恒温反应6-10小时，直至溶液呈深棕色；抽滤烘干得到所述二恶唑溴化物。
在本发明一实施例中，所述异硫氰芳基化合物的分子结构式为：
Figure PCTCN2019101491-appb-000004
所述酮基叠氮化合物的分子结构式为：
Figure PCTCN2019101491-appb-000005
所述二恶唑溴化物的分子结构式为：
Figure PCTCN2019101491-appb-000006
本发明还提供了一种有机发光器件，包括所述的有机发光材料。
在本发明一实施例中，所述的有机发光器件包括第一电极；空穴注入层，设于所述第一电极上；空穴传输层，设于所述空穴注入层上；发光层，设于所述空穴传输层上，所述发光层中具有所述有机发光材料；电子传输层，设于所述发光层上；电子注入层，设于所述电子传输层上；第二电极，设于所述电子注入层上。
有益效果
本发明的有机发光材料及其制备方法、有机发光器件，通过铃木反应的制备方法得到具有苯并菲衍生物的有机发光材料，即其具有良好的平面性和强烈的可见π-π*吸收能力，同时具有高量子产率的蓝光荧光发射能力，因此，具有大π共轭体系的苯并菲衍生物具有高效电子传输特性，其作为一种高效的吸电子基团会增加电荷迁移效率，有效提高了有机发光器件的发光效率。
附图说明
为了更清楚地说明本发明实施例中的技术方案，下面将对实施例描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
下面结合附图和实施例对本发明作进一步解释。
图1是本发明的有机发光材料通过循环伏安法测定的波形图。
图2是本发明的有机发光材料在四氢呋喃溶液中的荧光光谱图。
图3本发明实施例的有机发光器件结构图。
附图标记：
1有机发光器件；
11第一电极；              12空穴注入层；
13空穴传输层；            14发光层；
15电子传输层；     16电子注入层；
17第二电极。
本发明的实施方式
下面详细描述本发明的实施方式，所述实施方式的示例在附图中示出，其中自始至终相同或类似的标号表示相同或类似的元件或具有相同或类似功能的元件。下面通过参考附图描述的实施方式是示例性的，仅用于解释本发明，而不能理解为对本发明的限制。
在一实施例中，本发明的有机发光材料，包括苯并菲衍生物，其中一种苯并菲衍生物的分子结构式为：
Figure PCTCN2019101491-appb-000007
在上述的苯并菲衍生物结构中，其具有大π共轭体系，即其具有良好的平面性和强烈的可见π-π *吸收能力，同时具有高量子产率的蓝光荧光发射能力，因此，具有大π共轭体系的苯并菲衍生物具有高效电子传输特性，其作为一种高效的吸电子基团会增加电荷迁移效率，提高其发光效率。
本发明还提供了一种制备方法，用以制作具有苯并菲衍生物的所述有机发光材料，包括以下步骤。
提供苯并菲硼酸衍生物、二恶唑溴化物。
在提供苯并菲硼酸衍生物步骤中包括将苯并菲化合物溶解于二氯甲烷中，所述苯并菲化合物包括1,2-苯并菲、2,3,6,7-苯并菲、9.10-苯并菲、十二氢苯并菲中的至少一种。本实施例中，选择1,2-苯并菲作为示例，对本发明的制备方法作具体说明。首选需要形成1,2-苯并菲衍生物中间体，之后通过1,2-苯并菲衍生物中间体形成1,2-苯并菲硼酸衍生物，合成所述1,2-苯并菲硼酸衍生物的反应式如下：
Figure PCTCN2019101491-appb-000008
参见上述的1,2-苯并菲衍生物中间体的反应式，将苯并菲化合物溶解于二氯甲烷之后不断搅拌，并在室温下加入无水溴化氢的二氯甲烷溶液，反应3-12小时，得到第二反应液；向所述第二反应液中加入无水硫酸钠，并充分搅拌后静置，得到第三反应液；用二氯甲烷萃取所述第三反应液，之后用乙醇析出白色固体并烘干，得到苯并菲衍生物中间体，具体的为1,2-苯并菲衍生物中间体。
参见上述的1,2-苯并菲硼酸衍生物的反应式，将所述1,2-苯并菲衍生物中间体充分溶解于四氢呋喃溶液中，得到第四反应液，降温， 使温度保持在-70℃至-90℃，并滴加催化剂丁基锂，直至所述第四反应液呈黄色，反应2-3小时；向所述第四反应液中滴加硼酸三甲酯，直至所述第四反应液澄清，再反应1-3小时，得到第五反应液；向所述第五反应液中加入稀盐酸，并搅拌，析出白色固体，抽滤烘干得到苯并菲硼酸衍生物，具体的为1,2-苯并菲硼酸衍生物。
在提供二恶唑溴化物步骤中包括提供异硫氰芳基化合物、酮基叠氮化合物；本实施例中，所述异硫氰芳基化合物的分子结构式为：
Figure PCTCN2019101491-appb-000009
所述酮基叠氮化合物的分子结构式为：
Figure PCTCN2019101491-appb-000010
所述二恶唑溴化物的分子结构式为：
Figure PCTCN2019101491-appb-000011
合成所述二恶唑溴化物的反应式如下：
Figure PCTCN2019101491-appb-000012
之后在氩气的保护下，向烧瓶中依次加入异硫氰芳基化合物以四氢呋喃溶液，并加入铜粉，得到第二混合液；加热所述第二混合液至40℃，直至所述第二混合液呈蓝色；将酮基叠氮化合物溶于四氢呋喃溶液中，配制成酮基叠氮化合物溶液；将酮基叠氮化合物溶液滴加至所述第二混合液中，恒温反应6-10小时，直至溶液呈深棕色；抽滤烘干得到所述二恶唑溴化物。本实施例中，所述异硫氰芳基化合物和所述酮基叠氮化合物的摩尔比为1:1。
之后通过铃木反应制备得到具有苯并菲衍生物的所述有机发光材料。具有苯并菲衍生物的所述有机发光材料的反应式如下：
Figure PCTCN2019101491-appb-000013
参见具有苯并菲衍生物的所述有机发光材料的反应式，在氮气保护下，向圆底烧瓶中加入硼酸、苯并菲硼酸衍生物、二恶唑溴化物、碳酸钾、N,N-二甲基甲酰胺溶剂，持续搅拌1-3小时，得到第一混合液；将所述第一混合液的温度升高至40℃-70℃，向所述第一混合液中加入四三苯基磷钯，继续升高温度至80℃-100℃，反应24小时至 96小时，得到第一反应液；将所述第一反应液冷却至室温，抽滤并干燥得到所述有机发光材料。
制备完成具有苯并菲衍生物的所述有机发光材料后，对具有苯并菲衍生物的所述有机发光材料的性能进行分析：首先根据具有苯并菲衍生物的所述有机发光材料的分子结构式进行泛函分析和能级计算，其最高占有轨道(HOMO)能级为4.76eV和最低占有轨道(LUMO)能级为1.87eV，能级差2.89eV。最高占有轨道(HOMO)能级4.76低于氧化铟锡(氧化铟锡的导电基板的功函数为5.3)，因此，具有苯并菲衍生物的所述有机发光材料在理论上是符合有机发光器件中发光层的主体材料的功函数的要求，恶二唑对苯二恶唑的能级差是能有效增加器件发光效率和发光能力的。
之后将具有苯并菲衍生物的所述有机发光材料配置成0.1mol/L的电解质溶液，然后制成1×10 -6mol/L的四氢呋喃和具有苯并菲衍生物的所述有机发光材料的溶液，在氩气环境中进行100mV/s的电极扫描循环10次得到循环伏安法测定的波形图，如图1所示，可以看出根据EHOMO＝e(|E 1/2|+4.4)、ELUMO＝EHOMO-|Eg|；其中Eg＝1240/λ，由图2可以得出，波长λ＝429nm。计算具有苯并菲衍生物的所述有机发光材料的HOMO和LUMO值分别为4.76eV和1.87eV，其能级差可以有效地平衡电荷传输，由此再次证实了具有苯并菲衍生物的所述有机发光材料能作为发光层的材料用于有机发光器件。
如图3所示，本发明还提供了一种有机发光器件1，包括所述的 具有苯并菲衍生物的所述有机发光材料。本实施中，所述的有机发光器件包括第一电极11、空穴注入层12、空穴传输层13、发光层14、电子传输层15、电子注入层16以及第二电极17。其中，所述空穴注入层12设于所述第一电极11上；所述空穴传输层13设于所述空穴注入层12上；所述发光层14设于所述空穴传输层13上，所述发光层14中包括具有苯并菲衍生物的所述有机发光材料；所述电子传输层15设于所述发光层14上；所述电子注入层16设于所述电子传输层15上；所述第二电极17设于所述电子注入层16上。所述第一电极11为阳极，所述第二电极17为阴极。
以上仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种有机发光材料，其包括苯并菲衍生物。
  2. 根据权利要求1所述的有机发光材料，其中，其中一种苯并菲衍生物的分子结构为
    Figure PCTCN2019101491-appb-100001
  3. 一种制备方法，用以制作权利要求1所述的有机发光材料，其包括以下步骤：
    提供苯并菲硼酸衍生物、二恶唑溴化物；
    在氮气保护下，向圆底烧瓶中加入硼酸、所述苯并菲硼酸衍生物、所述二恶唑溴化物、碳酸钾、N,N-二甲基甲酰胺溶剂，持续搅拌1-3小时，得到第一混合液；
    将所述第一混合液的温度升高至40℃-70℃，向所述第一混合液中加入四三苯基磷钯，继续升高温度至80℃-100℃，反应24小时至96小时，得到第一反应液；
    将所述第一反应液冷却至室温，抽滤并干燥得到所述有机发光材料。
  4. 根据权利要求3所述的制备方法，其中，提供苯并菲硼酸衍生物的所述步骤包括
    将苯并菲化合物溶解于二氯甲烷中，不断搅拌，并在室温下加入无水溴化氢的二氯甲烷溶液，反应3-12小时，得到第二反应液；
    向所述第二反应液中加入无水硫酸钠，并充分搅拌后静置，得到第三反应液；
    用二氯甲烷萃取所述第三反应液，之后用乙醇析出白色固体并烘干，得到苯并菲衍生物中间体；
    将所述苯并菲衍生物中间体充分溶解于四氢呋喃溶液中，得到第四反应液，降温，使温度保持在-70℃至-90℃，并滴加催化剂丁基锂，直至所述第四反应液呈黄色，反应2-3小时；
    向所述第四反应液中滴加硼酸三甲酯，直至所述第四反应液澄清，再反应1-3小时，得到第五反应液；
    向所述第五反应液中加入稀盐酸，并搅拌，析出白色固体，抽滤烘干得到所述苯并菲硼酸衍生物。
  5. 根据权利要求4所述的制备方法，其中，所述苯并菲化合物包括1,2-苯并菲、2,3,6,7-苯并菲、9.10-苯并菲、十二氢苯并菲中的至少一种。
  6. 根据权利要求5所述的制备方法，其中，当所述苯并菲化合物为1,2-苯并菲时，所述苯并菲衍生物中间体的分子结构式为：
    Figure PCTCN2019101491-appb-100002
    所述苯并菲硼酸衍生物的分子结构式为：
    Figure PCTCN2019101491-appb-100003
  7. 根据权利要求5所述的制备方法，其中，提供二恶唑溴化物的所述步骤包括
    提供异硫氰芳基化合物、酮基叠氮化合物；
    在氩气的保护下，向烧瓶中依次加入异硫氰芳基化合物以四氢呋喃溶液，并加入铜粉，得到第二混合液；
    加热所述第二混合液至40℃，直至所述第二混合液呈蓝色；
    将酮基叠氮化合物溶于四氢呋喃溶液中，配制成酮基叠氮化合物溶液；
    将酮基叠氮化合物溶液滴加至所述第二混合液中，恒温反应6-10小时，直至溶液呈深棕色；
    抽滤烘干得到所述二恶唑溴化物。
  8. 根据权利要求7所述的制备方法，其中，
    所述异硫氰芳基化合物的分子结构式为：
    Figure PCTCN2019101491-appb-100004
    所述酮基叠氮化合物的分子结构式为：
    Figure PCTCN2019101491-appb-100005
    所述二恶唑溴化物的分子结构式为：
    Figure PCTCN2019101491-appb-100006
  9. 一种有机发光器件，其采用如权利要求1所述的有机发光材料。
  10. 根据权利要求9所述的有机发光器件，其包括
    第一电极；
    空穴注入层，设于所述第一电极上；
    空穴传输层，设于所述空穴注入层上；
    发光层，设于所述空穴传输层上，所述发光层采用所述有机发光材料；
    电子传输层，设于所述发光层上；
    电子注入层，设于所述电子传输层上；
    第二电极，设于所述电子注入层上。
PCT/CN2019/101491 2019-05-20 2019-08-20 有机发光材料及其制备方法、有机发光器件 Ceased WO2020232852A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US16/607,647 US11254687B2 (en) 2019-05-20 2019-08-20 Organic light-emitting material and manufacturing method thereof, and organic light-emitting device

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201910416911.5A CN110078681B (zh) 2019-05-20 2019-05-20 有机发光材料及其制备方法、有机发光器件
CN201910416911.5 2019-05-20

Publications (1)

Publication Number Publication Date
WO2020232852A1 true WO2020232852A1 (zh) 2020-11-26

Family

ID=67420848

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/101491 Ceased WO2020232852A1 (zh) 2019-05-20 2019-08-20 有机发光材料及其制备方法、有机发光器件

Country Status (3)

Country Link
US (1) US11254687B2 (zh)
CN (1) CN110078681B (zh)
WO (1) WO2020232852A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115975231A (zh) * 2023-02-14 2023-04-18 江苏振宁半导体研究院有限公司 一种可拉伸半导体薄膜的通用制备方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110078681B (zh) * 2019-05-20 2020-10-13 武汉华星光电半导体显示技术有限公司 有机发光材料及其制备方法、有机发光器件

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010241688A (ja) * 2007-07-07 2010-10-28 Idemitsu Kosan Co Ltd 非対称クリセン誘導体、有機ｅｌ素子用材料、有機ｅｌ素子用発光材料、及び、有機ｅｌ素子
CN101898996A (zh) * 2009-05-31 2010-12-01 清华大学 一种有机材料及其在有机电致发光器件中的应用
CN108586188A (zh) * 2018-06-01 2018-09-28 石家庄诚志永华显示材料有限公司 *衍生物、包含该*衍生物的材料和有机电致发光器件
CN110078681A (zh) * 2019-05-20 2019-08-02 武汉华星光电半导体显示技术有限公司 有机发光材料及其制备方法、有机发光器件

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100822569B1 (ko) 2000-09-07 2008-04-16 이데미쓰 고산 가부시키가이샤 유기 전계 발광 소자
KR101528241B1 (ko) * 2007-12-07 2015-06-15 삼성디스플레이 주식회사 방향족 복소환 화합물, 이를 포함한 유기막을 구비한 유기발광 소자 및 상기 유기발광 소자의 제조 방법
JP5495606B2 (ja) 2009-04-08 2014-05-21 キヤノン株式会社 新規縮合多環化合物およびそれを有する有機発光素子
US9647220B2 (en) * 2012-11-15 2017-05-09 Sony Corporation Organic multicolor light-emitting apparatus
CN104744450A (zh) * 2013-12-26 2015-07-01 东丽先端材料研究开发（中国）有限公司 芳香胺化合物、发光元件材料及发光元件

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010241688A (ja) * 2007-07-07 2010-10-28 Idemitsu Kosan Co Ltd 非対称クリセン誘導体、有機ｅｌ素子用材料、有機ｅｌ素子用発光材料、及び、有機ｅｌ素子
CN101898996A (zh) * 2009-05-31 2010-12-01 清华大学 一种有机材料及其在有机电致发光器件中的应用
CN108586188A (zh) * 2018-06-01 2018-09-28 石家庄诚志永华显示材料有限公司 *衍生物、包含该*衍生物的材料和有机电致发光器件
CN110078681A (zh) * 2019-05-20 2019-08-02 武汉华星光电半导体显示技术有限公司 有机发光材料及其制备方法、有机发光器件

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115975231A (zh) * 2023-02-14 2023-04-18 江苏振宁半导体研究院有限公司 一种可拉伸半导体薄膜的通用制备方法

Also Published As

Publication number Publication date
CN110078681B (zh) 2020-10-13
US11254687B2 (en) 2022-02-22
CN110078681A (zh) 2019-08-02
US20210403481A1 (en) 2021-12-30

Similar Documents

Publication Publication Date Title
Qiu et al. Novel 9, 9-dimethylfluorene-bridged D–π–A-type fluorophores with a hybridized local and charge-transfer excited state for deep-blue electroluminescence with CIE y∼ 0.05
Huang et al. Construction of efficient blue AIE emitters with triphenylamine and TPE moieties for non-doped OLEDs
CN107245079B (zh) 一种氮杂氧杂蒽酮类化合物及其在oled器件上的应用
CN101139317A (zh) 含咔唑单元的有机半导体材料及合成
CN103242298B (zh) 1,2,4-三氮唑类衍生物及其制备方法和应用及有机电致发光器件
CN106467529B (zh) 一种以9-芴酮为核心的有机电致发光材料及其应用
CN106220645B (zh) 一种基于单取代基-9-芴酮的化合物及其应用
CN109912578A (zh) 一种含螺芴结构的化合物及其在有机电致发光器件上的应用
CN105384613B (zh) 一种新的有机电致发光材料及其制备方法和应用
CN109574909A (zh) 一种以酮类结构为核心的有机化合物及其在oled器件中的应用
CN109912564A (zh) 一种以氰基氮杂苯为核心的化合物及其在oled器件上的应用
WO2020232852A1 (zh) 有机发光材料及其制备方法、有机发光器件
CN113683646B (zh) 含单碳硼烷类金属铂配合物及其制备方法、应用
CN104650066B (zh) 一种绿光材料的制备及其有机发光器件
CN102807554B (zh) 含萘、蒽、二苯并噻吩砜单元的有机半导体材料及其制备方法和应用
CN106800557B (zh) 一种二氧吩恶噻类衍生物及其制备方法和应用
CN106800567B (zh) 一种吖啶螺噻吨砜类衍生物及其制备方法和应用
CN106699731B (zh) 一种马来酰肼类衍生物及其制备方法和应用
CN117263893A (zh) 一种含有二甲基芴结构的有机化合物及包含其的有机电致发光器件
CN106467532B (zh) 一种以含氮五元杂环为核心的化合物及其在oled器件上的应用
CN109912494A (zh) 一种以氰基苯为核心的化合物及其在oled器件上的应用
CN107056726B (zh) 一种基于10,10-二芳基蒽酮的化合物及其在有机电致发光器件上的应用
CN1749254A (zh) 含杂原子双螺环材料及其合成方法和应用
CN112151685B (zh) 一种离子型主体材料及其在固态发光电化学池中的应用
CN109912495A (zh) 一种以氰基苯为核心的化合物及其在有机电致发光器件中的应用

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19930129

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19930129

Country of ref document: EP

Kind code of ref document: A1