WO2021189528A1 - 热活化延迟荧光材料及其合成方法、电致发光器件 - Google Patents

热活化延迟荧光材料及其合成方法、电致发光器件 Download PDF

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WO2021189528A1
WO2021189528A1 PCT/CN2020/083472 CN2020083472W WO2021189528A1 WO 2021189528 A1 WO2021189528 A1 WO 2021189528A1 CN 2020083472 W CN2020083472 W CN 2020083472W WO 2021189528 A1 WO2021189528 A1 WO 2021189528A1
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target compound
thermally activated
activated delayed
fluorescent material
delayed fluorescent
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PCT/CN2020/083472
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王彦杰
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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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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
    • C07C225/22—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • 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
    • 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
    • H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings
    • 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
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1011—Condensed systems

Definitions

  • the invention relates to the field of display, in particular to a thermally activated delayed fluorescent material, a synthesis method thereof, and an electroluminescent device.
  • OLED Organic light-emitting diode
  • Samsung and LG have implemented OLED applications on mobile phones.
  • the usual luminescent layer material consists of host and guest luminescent materials, and the luminous efficiency and lifetime of luminescent materials are two important indicators of the quality of luminescent materials.
  • Early OLED light-emitting materials were traditional fluorescent materials. Since the ratio of singlet and triplet excitons in OLED is 1:3, traditional fluorescent materials can only use singlet excitons to emit light. Therefore, the traditional fluorescent material OLED The theoretical internal quantum efficiency is 25%. Due to the spin-orbit coupling effect of heavy atoms, metal complex phosphorescent materials can achieve 100% utilization of singlet excitons and triplet excitons; and are now also used in red and green OLED displays. However, phosphorescent materials usually use heavy metals such as Ir, Pt, Os and other precious metals, which are not only costly, but also more toxic. In addition, efficient and long-life phosphorescent metal complex materials are still a great challenge.
  • Adachi et al. proposed a pure organic light-emitting molecule with a "thermal activated delayed fluorescence" (TADF) mechanism.
  • TADF thermal activated delayed fluorescence
  • the molecule has a smaller minimum singlet state and triplet energy difference ( ⁇ EST).
  • RISC anti-system crossing
  • RISC anti-system crossing
  • the TADF material has rich structural designs, and most of its physical properties can be easily adjusted to obtain high-efficiency and long-life organic light-emitting materials that meet the requirements.
  • TADF materials small ⁇ EST and high photoluminescence quantum yield (PLQY) are necessary conditions for the preparation of high-efficiency OLEDs.
  • PLQY photoluminescence quantum yield
  • green and sky blue TADF materials have achieved external quantum efficiency (EQE) of more than 30%; however, long-wavelength TADF materials cannot achieve excellent device performance due to the energy gap law.
  • the purpose of the present invention is to solve the technical problems in the prior art that the long-wavelength thermally activated delayed fluorescent material has a large difference between the lowest singlet state and triplet energy level and poor device performance.
  • the present invention provides a thermally activated delayed fluorescent material, which is a target compound synthesized by the reaction of an electron donor and an electron acceptor.
  • the target compound has a D n -A molecular structure, and n is 1 or 2 or 3; Wherein in the molecular structure, D is an electron donor, and A is an electron acceptor.
  • the electron acceptor is any one of the following structures:
  • the group R in the electron acceptor is at least one of an alkyl group, an alkoxy group, an aryl group, and a substituted aryl group.
  • the electron donor is any one of the following structures or derivatives thereof:
  • the present invention also provides a method for synthesizing a thermally activated delayed fluorescent material, which includes the following steps: a reaction solution preparation step, where an electron donor, an electron acceptor and a catalyst are placed in a reaction vessel to obtain a reaction solution; In the compound synthesis step, fully react at a temperature of 50°C to 100°C to obtain a mixed solution containing the target compound produced by the reaction; in the extraction step, the mixed solution is cooled to room temperature, and the mixed solution is extracted. The target compound in the solution; and a purification treatment step of the target compound, which separates and purifies the target compound to obtain a thermally activated delayed fluorescent material.
  • the reaction solution preparation step includes the following steps: the electron acceptor solution preparation step is to combine 2,8,14-tribromo-6,6,12,12,18,18-hexamethyl-trimeric ketone , 4-(Diphenylamino)-phenylboronic acid is added to the Schlenk bottle, and toluene and potassium carbonate aqueous solution are added, and the reaction is fully stirred at room temperature to obtain an electron acceptor solution.
  • the reaction solution is cooled to room temperature and subjected to multiple extractions and water washing; after multiple extractions, the organic phases are combined to obtain the target compound; in the purification treatment step of the target compound, use
  • the eluent is used to purify the target compound by silica gel column chromatography; wherein the eluent is dichloromethane and petroleum ether, and the volume ratio of the dichloromethane to the petroleum ether is 1:1.
  • the present invention also provides an electroluminescent device, which in turn includes a substrate layer, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode layer; wherein the material used for the light emitting layer is The thermally activated delayed material described above.
  • the technical effect of the present invention is that through the combination of different functional groups, a series of deep red photothermally activated delayed fluorescent materials with significant thermally activated delayed fluorescence characteristics are synthesized, and the synthesis rate is relatively high.
  • thermally activated delayed fluorescent materials It accounts for a high proportion in the whole synthesized product, and its photoluminescence quantum yield is high, thereby improving the organic electroluminescence device, so that the organic electroluminescence device with the deep red photothermal activation delayed fluorescent material has a higher The luminous efficiency and brightness.
  • FIG. 1 is a flowchart of a method for synthesizing thermally activated delayed fluorescent materials according to an embodiment of the present invention
  • FIG 2 is an emission spectrum diagram of the thermally activated delayed fluorescent material according to an embodiment of the present invention.
  • FIG. 3 is a schematic diagram of the structure of the electroluminescent device according to an embodiment of the application.
  • Substrate layer 2. Hole injection layer; 3. Hole transport layer; 4. Light emitting layer; 5. Electron transport layer; 6. Cathode layer.
  • the "above” or “below” of the first feature of the second feature may include direct contact between the first and second features, or may include the first and second features Not in direct contact but through other features between them.
  • the "above”, “above” and “above” of the first feature on the second feature include the first feature directly above and obliquely above the second feature, or it simply means that the first feature is higher in level than the second feature.
  • the “below”, “below” and “below” of the second feature of the first feature include the first feature directly below and obliquely below the second feature, or it simply means that the level of the first feature is smaller than the second feature.
  • This embodiment provides a thermally activated delayed fluorescent material, which is a target compound synthesized by the reaction of an electron donor and an electron acceptor, and the target compound is a D n -A molecular structure, and n is 1 or 2 or 3; In the molecular structure, D is an electron donor, and A is an electron acceptor.
  • the structure of the target compound is as follows:
  • the electron acceptor is any one of the following structures:
  • the group R in the electron acceptor is at least one of an alkyl group, an alkoxy group, an aryl group, and a substituted aryl group.
  • the electron donor is any one of the following structures or derivatives thereof:
  • Table 1 shows the measured parameters such as the lowest singlet state (S1) and lowest triplet energy level (T1) of the target compound:
  • the photoluminescence spectrum of the target compound in the toluene solution at room temperature is shown in FIG. 2.
  • long-wavelength TADF materials have a molecular structure in which electron donors (D) and electron acceptors (A) are combined, and by introducing large flat and rigid acceptors, they can inhibit molecular vibration and reduce molecular non-radiative transitions, thereby increasing the molecular structure.
  • the radiation transition rate is high, and high photoluminescence fluorescence quantum efficiency (PLQY) is obtained.
  • the long-wavelength thermally activated delayed fluorescent molecule containing the telomerone receptor contains a carbonyl structure and has a super large plane, so that the molecule has a high intersystem crossover rate constant and anti-intersystem crossover.
  • the rate constant can effectively suppress the decrease of the radiation transition rate due to the energy gap rules, thereby obtaining high PLQY.
  • the super large plane exhibits great rigidity, which increases the stability of the TADF material and can increase the life of the device.
  • this embodiment also provides a method for synthesizing thermally activated delayed fluorescent materials, including steps S1 to S4, and the synthesis route is as follows:
  • the electron donor, the electron acceptor and the catalyst are placed in the reaction vessel to obtain the reaction solution.
  • the electron acceptor solution preparation step is to mix 8mmol ⁇ 12mmol of 2,8,14-tribromo-6,6,12,12,18,18-hexamethyl-tarinone, 30mmol ⁇ 35mmol 4-(diphenylamino)-phenylboronic acid is added to a Schlenk bottle of 100ml ⁇ 200ml, 25ml ⁇ 35ml of toluene and 8ml ⁇ 12ml of potassium carbonate aqueous solution are added, the reaction is fully stirred at room temperature, and argon is used for pumping Ventilate to obtain an electron acceptor solution.
  • the target compound synthesis step is to fully react under the condition of a temperature of 50° C.-100° C. to obtain a mixed solution, and the mixed solution contains the target compound produced by the reaction. 0.2 mmol-0.5 mmol of palladium tetrakistriphenylphosphorus is added to the reaction solution and fully reacted for 24 hours. In this embodiment, the reaction is fully carried out under the condition of a temperature of 80° C. to obtain a mixed solution in which the target compound produced by the reaction is contained. 0.4 mmol of palladium tetrakistriphenylphosphorus was added to the reaction solution, and the reaction was fully refluxed for 24 hours under the temperature condition of 80°C.
  • the mixed solution is cooled to room temperature, and the target compound in the mixed solution is extracted.
  • the reaction solution was cooled to room temperature, and dichloromethane (DCM) was used for multiple extractions and washings with water.
  • DCM dichloromethane
  • three extractions and washings with water are preferred. After three extractions, the organic phases are combined to obtain the target compound.
  • the target compound purification treatment step is to separate and purify the target compound to obtain a thermally activated delayed fluorescent material. Purify the target compound by silica gel column chromatography using eluent, wherein the eluent is dichloromethane and petroleum ether, and the volume ratio of dichloromethane to petroleum ether is 1:1, The dichloromethane was the solvent in the column chromatography step. The target compound was separated and purified to obtain 11.40g of a dark red powder with a yield of 92%. The results of the hydrogen nuclear magnetic spectrum and the carbon spectrum were: HRMS[M +H]+calcd.for C 90 H 69 N 3 O 3 : 1239.5339; found: 1239.5356.
  • the technical effect of the present invention is that through the combination of different functional groups, a series of deep red photothermally activated delayed fluorescent materials with significant thermally activated delayed fluorescence characteristics are synthesized, and the synthesis rate is relatively high.
  • thermally activated delayed fluorescent materials It accounts for a high proportion in the whole synthesized product, and its photoluminescence quantum yield is high.
  • this embodiment also provides an electroluminescent device, which includes a substrate layer 1, a hole injection layer 2, a hole transport layer 3, a light emitting layer 4, an electron transport layer 5, and a cathode from bottom to top.
  • a 40 nm layer of 4,4'-cyclohexylbis[N,N-bis(4-methylphenyl)aniline]-TAPC was spin-coated on the hole injection layer 2 to obtain the hole transport layer 3.
  • the hole transport layer 3 is spin-coated with a layer of 40 nm of the aforementioned thermally activated retardation material and 5% of the host 4,4'-N,N'-dicarbazolebiphenyl-CBP to obtain a light-emitting layer 4.
  • Tm3PyPB 1,3,5-tris(3-(3-pyridyl)phenyl)benzene
  • the current-brightness-voltage characteristics of the device are measured by a Keithley source measurement system (Keithley 2400 Sourcemeter, Keithley 2000 Currentmeter) with a calibrated silicon photodiode.
  • the electroluminescence spectrum is measured by the SPEX CCD3000 spectrometer from JY, France. All measurements are done in the atmosphere at room temperature.
  • the performance data of the electroluminescent device is shown in Table 2 below.
  • Table 2 shows the measured parameters such as the highest brightness and maximum external quantum efficiency of the electroluminescent device:
  • the electroluminescent device made by using deep red light and thermally activated delayed fluorescent material has high luminous efficiency and brightness, high production efficiency and long service life.
  • the technical effect of the present invention is that through the combination of different functional groups, a series of deep red photothermally activated delayed fluorescent materials with significant thermally activated delayed fluorescence characteristics are synthesized, and the synthesis rate is relatively high.
  • thermally activated delayed fluorescent materials It accounts for a high proportion in the whole synthesized product, and its photoluminescence quantum yield is high, thereby improving the organic electroluminescence device, so that the organic electroluminescence device with the deep red photothermal activation delayed fluorescent material has a higher The luminous efficiency and brightness.

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Abstract

本发明公开了一种热活化延迟荧光材料及其合成方法、电致发光器件，上述热活化延迟荧光材料为由电子给体和电子受体反应合成的目标化合物，所述目标化合物为D n-A分子结构，n为1或2或3；其中所述分子结构中D为电子给体，A为电子受体。

Description

热活化延迟荧光材料及其合成方法、电致发光器件 技术领域
本发明涉及显示领域，特别涉及一种热活化延迟荧光材料及其合成方法、电致发光器件。
背景技术
有机发光二极管(organic lighting-emitting diode,OLED)，由于主动发光、可视角度大、相应速度快、温度适应范围宽、驱动电压低、功耗小、亮度大、生产工艺简单、轻薄、且可以柔性显示等优点，在OLED显示和照明领域表现出巨大的应用前景，吸引了科研工作者和公司的关注。目前，三星、LG已经实现OLED应用在手机上。
在OLED中，发光层材料的优劣是OLED能否产业化起决定作用。通常的发光层材料由主体和客体发光材料，而发光材料的发光效率和寿命是发光材料好坏的两个重要指标。早期的OLED发光材料为传统荧光材料，由于在OLED中单重态和三重态的激子比例为1:3，而传统荧光材料只能利用单重态激子发光，因此，传统荧光材料的OLED理论内量子效率为25％。金属配合物磷光材料由于重原子的自旋轨道耦合效应，使得其能够实现单重态激子和三重态激子的100％利用率；并且现在也已经用在红光和绿光OLED显示上。但是，磷光材料通常要使用重金属Ir、Pt、Os等贵重金属，不仅成本高，而且毒性较大。此外，高效、长寿命的磷光金属配合物材料仍旧是极大的挑战。
2012年，Adachi等人提出了“热活化延迟荧光”(TADF)机理的纯有机发光分子，通过合理的D-A结构分子设计，使得分子具有较小的最低单重态和三重能级差(ΔEST)，这样三重态激子可以通过反系间窜越(RISC)回到单重态，再通过辐射跃迁至基态而发光，从而能够同时利用单、三重态激子，可以实现激子的100％的利用率，同时不需要重金属的参与。并且TADF材料结构设计丰富，其材料大部分物理性质容易调节，以获得满足要求的高效、长寿命的有机发光材料。
对于TADF材料，小的ΔEST以及高的光致发光量子产率(PLQY)是制备高效率OLED的必要条件。目前，绿光和天蓝光TADF材料已经获得超过30％的外量子效率(EQE)；但是长波长TADF材料由于能隙规则(Energy gap law)，无法获得优异的器件性能。
技术问题
本发明的目的在于，解决现有技术中长波长热活化延迟荧光材料的最低单重态和三重能级差较大，器件性能不佳的技术问题。
技术解决方案
为实现上述目的，本发明提供一种热活化延迟荧光材料，其为由电子给体和电子受体反应合成的目标化合物，所述目标化合物为D n-A分子结构，n为1或2或3；其中所述分子结构中D为电子给体，A为电子受体。
进一步地，所述目标化合物的结构如下：
Figure PCTCN2020083472-appb-000001
进一步地，所述电子受体为如下结构中的任一种：
Figure PCTCN2020083472-appb-000002
Figure PCTCN2020083472-appb-000003
进一步地，所述电子受体中基团R为烷基、烷氧基、芳基、取代芳基中的至少一种。
进一步地，所述电子给体为如下结构中的任一种或其衍生物：
Figure PCTCN2020083472-appb-000004
为实现上述目的，本发明还提供一种热活化延迟荧光材料的合成方法，包括以下步骤：反应液配制步骤，将电子给体、电子受体以及催化剂置于反应容器中，获得反应液；目标化合物合成步骤，在温度为50℃-100℃的条件下充分反应，获得混合溶液，所述混合溶液中具有反应生成的目标化合物；萃取步骤，将所述混合溶液冷却至室温，萃取所述混合溶液中的目标化合物；以及目标化合物纯化处理步骤，分离纯化所述目标化合物，获得热活化延迟荧光材料。
进一步地，所述反应液配制步骤包括以下步骤：电子受体溶液制备步骤，将2,8,14-三溴-6,6,12,12,18,18-六甲基-三聚萘酮、4-(二苯基氨基)-苯硼酸加入至Schlenk瓶中，并加入甲苯以及碳酸钾水溶液，在室温下充分搅拌反应，获得电子受体溶液。
进一步地，在所述目标化合物合成步骤中，将四三苯基磷钯加入至所述反应液中，充分反应24小时。
进一步地，在所述萃取步骤中，将反应液冷却至室温，并进行多次萃取及水洗；多次萃取后合并有机相，得到所述目标化合物；在所述目标化合物纯化处理步骤中，使用淋洗液，通过硅胶柱层析方法纯化所述目标化合物；其中，所述淋洗液为二氯甲烷和石油醚，所述二氯甲烷和所述石油醚的体积比为1:1。
为实现上述目的，本发明还提供一种电致发光器件，依次包括衬底层、空穴注入层、空穴传输层、发光层、电子传输层以及阴极层；其中，所述发光层所用材料为前文所述的热活化延迟材料。
有益效果
本发明的技术效果在于，通过不同官能团的搭配，合成一系列具有显著热激活延迟荧光特性的深红光热活化延迟荧光材料，其合成率较高，在合成的产物中，热活化延迟荧光材料在整个合成的产物中的占比高，其光致发光量子产率高，进而改进了有机电致发光器件，使得具有该深红光热活化延迟荧光材料的有机电致发光器件其具有较高的发光效率和亮度。
附图说明
下面结合附图，通过对本申请的具体实施方式详细描述，将使本申请的技术方案及其它有益效果显而易见。
图1为本发明实施例所述热活化延迟荧光材料的合成方法的流程图；
图2为本发明实施例所述热活化延迟荧光材料的发射光谱图；
图3为本申请实施例所述电致发光器件的结构示意图。
部分组件标识如下：
1、衬底层；2、空穴注入层；3、空穴传输层；4、发光层；5、电子传输层；6、阴极层。
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。
在本申请的描述中，需要理解的是，术语“上”、“下”等指示的方位或位置关系为基于附图所示的方位或位置关系，仅是为了便于描述本申请和简化描述，而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作，因此不能理解为对本申请的限制。
在本申请中，除非另有明确的规定和限定，第一特征在第二特征之“上”或之“下”可以包括第一和第二特征直接接触，也可以包括第一和第二特征不是直接接触而是通过它们之间的另外的特征接触。而且，第一特征在第二特征“之上”、“上方”和“上面”包括第一特征在第二特征正上方和斜上方，或仅仅表示第一特征水平高度高于第二特征。第一特征在第二特征“之下”、“下方”和“下面”包括第一特征在第二特征正下方和斜下方，或仅仅表示第一特征水平高度小于第二特征。
下文的公开提供了许多不同的实施方式或例子用来实现本申请的不同结构。为了简化本申请的公开，下文中对特定例子的部件和设置进行描述。当然，它们仅仅为示例，并且目的不在于限制本申请。此外，本申请可以在不同例子中重复参考数字和/或参考字母，这种重复是为了简化和清楚的目的，其本身不指示所讨论各种实施方式和/或设置之间的关系。
本实施例提供一种热活化延迟荧光材料，其为由电子给体和电子受体反应合成的目标化合物，所述目标化合物为D n-A分子结构，n为1或2或3；其中所述分子结构中D为电子给体，A为电子受体。
所述目标化合物的结构如下：
Figure PCTCN2020083472-appb-000005
所述电子受体为如下结构中的任一种：
Figure PCTCN2020083472-appb-000006
其中，所述电子受体中基团R为烷基、烷氧基、芳基、取代芳基中的至少一种。
所述电子给体为如下结构中的任一种或其衍生物：
Figure PCTCN2020083472-appb-000007
表1为所测得的目标化合物的最低单重态(S1)和最低三重态能级(T1)等参数：
Figure PCTCN2020083472-appb-000008
所述目标化合物在室温下，甲苯溶液中的光致发光光谱如图2所示。
一般长波长TADF材料具有电子给体(D)和电子受体(A)相结合的分子结构，并且通过引入大平面、刚性受体来抑制分子的振动、降低分子的非辐射跃迁，从而提高分子的辐射跃迁速率，获得高的光致发光荧光量子效率(PLQY)。本实施例中含三聚萘酮类受体的长波长热活化延迟荧光分子的受体含有羰基结构，同时并且具有超大平面，使得分子具有高的系间窜越速率常数和反系间窜越速率常数，能够有效抑制由于能隙规则导致的辐射跃迁速率的降低，从而获得高的PLQY。同时超大平面表现出大的刚性，增加了TADF材料的稳定性，能够提高器件的寿命。
如图1所示，本实施例还提供一种热活化延迟荧光材料的合成方法，包括步骤S1～S4，合成路线如下所示：
Figure PCTCN2020083472-appb-000009
S1反应液配制步骤，将电子给体、电子受体以及催化剂置于反应容器中，获得反应液。具体包括以下步骤：电子受体溶液制备步骤，将8mmol～12mmol的2,8,14-三溴-6,6,12,12,18,18-六甲基-三聚萘酮、30mmol～35mmol的4-(二苯基氨基)-苯硼酸加入至100ml～200ml的Schlenk瓶中，并加入25ml～35ml的甲苯以及8ml～12ml的碳酸钾水溶液，在室温下充分搅拌反应，并用氩气进行抽换气，获得电子受体溶液。在本实施例中，将7.47g，10mmol的2,8,14-三溴-6,6,12,12,18,18-六甲基-三聚萘酮、3.18g，33mmol的4-(二苯基氨基)-苯硼酸加入至100ml的Schlenk瓶中，并加入30ml的甲苯以及2.5M，10ml的碳酸钾水溶液，在室温下充分搅拌反应，并用氩气进行抽换气，获得电子受体溶液
S2目标化合物合成步骤，在温度为50℃-100℃的条件下充分反应，获得混合溶液，所述混合溶液中具有反应生成的目标化合物。将0.2mmol～0.5mmol的四三苯基磷钯加入至所述反应液中，充分反应24小时。在本实施例中，在温度为80℃的条件下充分反应，获得混合溶液，所述混合溶液中具有反应生成的目标化合物。将0.4mmol的四三苯基磷钯加入至所述反应液中，在80℃的温度条件下充分回流反应24小时。
S3萃取步骤，将所述混合溶液冷却至室温，萃取所述混合溶液中的目标化合物。具体地，将反应液冷却至室温，采用二氯甲烷(DCM)进行多次萃取及水洗，在本实施例中，优选为三次萃取及水洗，三次萃取后合并有机相，得到所述目标化合物
S4目标化合物纯化处理步骤，分离纯化所述目标化合物，获得热活化延 迟荧光材料。使用淋洗液，通过硅胶柱层析方法纯化所述目标化合物，其中，所述淋洗液为二氯甲烷和石油醚，所述二氯甲烷和所述石油醚的体积比为1:1，所述二氯甲烷为所述柱层析步骤中的溶剂，分离纯化所述目标化合物，获得一深红色粉末11.40g，产率为92％，核磁氢谱、碳谱的结果为：HRMS[M+H]+calcd.for C 90H 69N 3O 3:1239.5339；found:1239.5356。
本发明的技术效果在于，通过不同官能团的搭配，合成一系列具有显著热激活延迟荧光特性的深红光热活化延迟荧光材料，其合成率较高，在合成的产物中，热活化延迟荧光材料在整个合成的产物中的占比高，其光致发光量子产率高。
如图3所示，本实施例还提供一种电致发光器件，从下往上依次包括衬底层1、空穴注入层2、空穴传输层3、发光层4、电子传输层5以及阴极层6，其中，发光层4所用材料为前文所述的热活化延迟材料。
在清洗过后的衬底层1上旋涂一层30nm的2,3,6,7,10,11-六氰基-1,4,5,8,9,12-六氮杂苯并菲-HATCN，获得一空穴注入层2，衬底层1的材质为玻璃和导电玻璃(ITO)。
在空穴注入层2上旋涂一层40nm的4,4'-环己基二[N,N-二(4-甲基苯基)苯胺]-TAPC，获得空穴传输层3。
在空穴传输层3上旋涂一层40nm的前文所述的热活化延迟材料以及5％的主体4,4’-N,N’-二咔唑联苯-CBP，获得一发光层4。
在高真空条件下，在发光层4上蒸镀一层40nm的1,3,5-三(3-(3-吡啶基)苯基)苯(Tm3PyPB)，获得一电子传输层5。
在高真空条件下，在电子传输层5上蒸镀一层1nm的氟化锂和100nm的铝，获得一阴极层6，最终制成一电致发光器件。
器件的电流-亮度-电压特性是由带有校正过的硅光电二极管的Keithley源测量系统(Keithley 2400 Sourcemeter、Keithley 2000 Currentmeter)完成的，电致发光光谱是由法国JY公司SPEX CCD3000光谱仪测量的，所有测量均在室温大气中完成。
所述电致发光器件的性能数据如下表2所示。
表2为所测得的电致发光器件的最高亮度、最大外量子效率等参数：
Figure PCTCN2020083472-appb-000010
利用深红光热活化延迟荧光材料制作而成的电致发光器件具有较高的发光效率和亮度，制作效率高，使用寿命长。
本发明的技术效果在于，通过不同官能团的搭配，合成一系列具有显著热激活延迟荧光特性的深红光热活化延迟荧光材料，其合成率较高，在合成的产物中，热活化延迟荧光材料在整个合成的产物中的占比高，其光致发光量子产率高，进而改进了有机电致发光器件，使得具有该深红光热活化延迟荧光材料的有机电致发光器件其具有较高的发光效率和亮度。
在上述实施例中，对各个实施例的描述都各有侧重，某个实施例中没有详述的部分，可以参见其他实施例的相关描述。
以上对本申请实施例所提供的一种热活化延迟荧光材料及其合成方法、电致发光器件进行了详细介绍，本文中应用了具体个例对本申请的原理及实施方式进行了阐述，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 (10)

  1. 一种热活化延迟荧光材料，其为由电子给体和电子受体反应合成的目标化合物，所述目标化合物为D n-A分子结构，n为1或2或3；其中所述分子结构中D为电子给体，A为电子受体。
  2. 如权利要求1所述的热活化延迟荧光材料，其中，
    所述目标化合物的结构如下：
    Figure PCTCN2020083472-appb-100001
  3. 如权利要求1所述的热活化延迟荧光材料，其中，
    所述电子受体为如下结构中的任一种：
    Figure PCTCN2020083472-appb-100002
  4. 如权利要求3所述的热活化延迟荧光材料，其中，
    所述电子受体中基团R为烷基、烷氧基、芳基、取代芳基中的至少一种。
  5. 如权利要求1所述的热活化延迟荧光材料，其中，
    所述电子给体为如下结构中的任一种或其衍生物：
    Figure PCTCN2020083472-appb-100003
  6. 一种热活化延迟荧光材料的合成方法，其包括以下步骤：
    反应液配制步骤，将电子给体、电子受体以及催化剂置于反应容器中，获得反应液；
    目标化合物合成步骤，在温度为50℃-100℃的条件下充分反应，获得混合溶液，所述混合溶液中具有反应生成的目标化合物；
    萃取步骤，将所述混合溶液冷却至室温，萃取所述混合溶液中的目标化合物；以及
    目标化合物纯化处理步骤，分离纯化所述目标化合物，获得热活化延迟荧光材料。
  7. 如权利要求6所述的热活化延迟荧光材料的合成方法，其中，
    所述反应液配制步骤包括以下步骤：
    电子受体溶液制备步骤，将2,8,14-三溴-6,6,12,12,18,18-六甲基-三聚萘酮、4-(二苯基氨基)-苯硼酸加入至Schlenk瓶中，并加入甲苯以及碳酸钾水溶液，在室温下充分搅拌反应，获得电子受体溶液。
  8. 如权利要求6所述的热活化延迟荧光材料的合成方法，其中，
    在所述目标化合物合成步骤中，将四三苯基磷钯加入至所述反应液中，充分反应24小时。
  9. 如权利要求6所述的热活化延迟荧光材料的合成方法，其中，
    在所述萃取步骤中，
    将反应液冷却至室温，并进行多次萃取及水洗；
    多次萃取后合并有机相，得到所述目标化合物；
    在所述目标化合物纯化处理步骤中，
    使用淋洗液，通过硅胶柱层析方法纯化所述目标化合物；
    其中，所述淋洗液为二氯甲烷和石油醚，所述二氯甲烷和所述石油醚的体积比为1:1。
  10. 一种电致发光器件，其依次包括衬底层、空穴注入层、空穴传输层、发光层、电子传输层以及阴极层；其中，所述发光层所用材料为如权利要求1所述的热活化延迟材料。
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