WO2021103298A1 - 热活化延迟荧光材料及其制备方法和电致发光器件 - Google Patents

热活化延迟荧光材料及其制备方法和电致发光器件 Download PDF

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WO2021103298A1
WO2021103298A1 PCT/CN2020/071737 CN2020071737W WO2021103298A1 WO 2021103298 A1 WO2021103298 A1 WO 2021103298A1 CN 2020071737 W CN2020071737 W CN 2020071737W WO 2021103298 A1 WO2021103298 A1 WO 2021103298A1
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thermally activated
activated delayed
delayed fluorescent
fluorescent material
compound
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罗佳佳
严舒星
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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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Definitions

  • the present invention relates to the field of display technology, in particular to a thermally activated delayed fluorescence (TADF) material, a preparation method thereof, and an electroluminescent device.
  • TADF thermally activated delayed fluorescence
  • OLED display devices require no backlight source for active light emission, high luminous efficiency, large viewing angle, fast response speed, large temperature adaptation range, relatively simple production and processing technology, and drive
  • the advantages of low voltage, low energy consumption, lighter and thinner, flexible display and huge application prospects have attracted the attention of many researchers.
  • the existing OLED display device usually includes a substrate, an anode provided on the substrate, an organic light emitting layer provided on the anode, an electron transport layer provided on the organic light emitting layer, and a cathode provided on the electron transport layer. When working, it emits holes from the anode and electrons from the cathode to the organic light-emitting layer, combines these electrons and holes to generate exciting electron-hole pairs, and converts the exciting electron-hole pairs from the excited state to the ground state Realize luminescence.
  • the light-emitting guest material that plays a leading role is very important.
  • the light-emitting guest materials used in early OLEDs were fluorescent materials. Since the ratio of singlet and triplet excitons in OLEDs is 1:3, the theoretical internal quantum efficiency (IQE) of OLEDs based on fluorescent materials is only It can reach 25%, which greatly limits the application of fluorescent electroluminescent devices. Due to the spin-orbit coupling of heavy atoms, heavy metal complex phosphorescent materials can simultaneously utilize singlet and triplet excitons to achieve 100% IQE. However, the commonly used heavy metals are precious metals such as Ir, Pt, etc., which are costly, and the heavy metal complex phosphorescent light-emitting materials still need a breakthrough in blue light materials.
  • TADF organic thermally activated delayed fluorescence
  • TADF materials For TADF materials, fast reverse intersystem-crossing constant (kRISC) and high photoluminescence quantum yield (PLQY) are necessary conditions for the preparation of high-efficiency OLEDs. At present, TADF materials with the above conditions are still relatively scarce compared to heavy metal Ir complexes. Due to the very broad spectrum of the TADF material and the exciton lifetime in the order of microseconds, its application in mass production device structures is greatly restricted.
  • the purpose of the present invention is to provide a thermally activated delayed fluorescence (TADF) material, as the main body of the green light-emitting guest, using the 100% internal quantum efficiency of the TADF material, so that the fluorescent device can reach the phosphorescent device (using phosphorescent The efficiency of heavy metal complexes), while solving the problems of excessively wide spectrum and long exciton lifetime, and overcoming the problem of poor color gamut of directly using TADF luminescent materials, in order to break through the UDC patent blockade on heavy metal phosphorescent complexes, and greatly To reduce costs.
  • the light-emitting materials provided by the present invention are used to prepare a series of high-performance TADF organic light-emitting diodes (OLED).
  • the present invention provides a thermally activated delayed fluorescence (TADF) material, which includes a compound composed of an acceptor A and a donor D, and the compound has the general structural formula shown in Formula 1:
  • TADF thermally activated delayed fluorescence
  • the receptor A is selected from any one of the following structural formulas:
  • the donor D is the following structural formula:
  • the present invention also provides a method for preparing a thermally activated delayed fluorescence (TADF) material, which includes the following steps:
  • Step S1 In an alkali-containing solution, the compound AX and the compound DH are reacted at a first temperature for a first period of time in the presence of a catalyst to obtain a reaction solution, wherein the X is a halogen, and the A is the following structural formula Either:
  • the D is the following structural formula:
  • Step S2 cooling the reaction liquid to a second temperature to obtain a mixture
  • Step S3 Separate the thermally activated delayed fluorescence (TADF) material from the mixture, including a compound composed of an acceptor A and a donor D, and the compound has the general structural formula shown in Formula 1:
  • TADF thermally activated delayed fluorescence
  • the first temperature is 80° C. to 150° C.
  • the first time period is 36 hours to 60 hours.
  • the second temperature is room temperature.
  • the solution in the preparation method of the thermally activated delayed fluorescence (TADF) material, in the step S1, the solution is toluene, and the alkali is sodium tert-butylate. , NaOtBu), and the catalyst includes palladium acetate and tri-tert-butylphosphine tetrafluoroborate.
  • the step S2 further includes extracting the reaction solution through dichloromethane several times and combining the organic phases to obtain the Said mixture.
  • the step S3 is to use column chromatography for separation, and the eluent used in the column chromatography Dichloromethane: n-hexane with a volume ratio of 1:1.
  • the step S1 is performed in an inert environment.
  • the present invention also provides an electroluminescent device, comprising: a base layer; a hole injection layer located on the base layer; a hole transport layer located on the hole injection layer; a light emitting layer located on the hole On the transport layer; the electron transport layer is located on the light-emitting layer; and the cathode layer is located on the electron transport layer, wherein the light-emitting layer includes the thermally activated delayed fluorescence (TADF) material provided by the present invention.
  • TADF thermally activated delayed fluorescence
  • the material of the base layer includes ITO;
  • the material of the hole injection layer includes 2,3,6,7,10,11-hexacyano -1,4,5,8,9,12-hexaazatriphenylene hexacarbonitrile (HATCN);
  • the material of the hole transport layer includes 4,4',4"-tris(carbazole-9- Base) triphenylamine (4,4',4"-Tris(carbazol-9-yl)-triphenylamine, TCTA);
  • the material of the electron transport layer includes 1,3,5-tris(3-(3-pyridyl) ) Phenyl) benzene (Tm3PyPB); and the material of the cathode layer includes lithium fluoride and aluminum.
  • the purpose of the present invention is to provide a thermally activated delayed fluorescence (TADF) material, as the main body of the green light-emitting guest, using the 100% internal quantum efficiency of the TADF material, so that the fluorescent device can reach the phosphorescent device (using phosphorescent The efficiency of heavy metal complexes), while solving the problems of excessively wide spectrum and long exciton lifetime, and overcoming the problem of poor color gamut of directly using TADF luminescent materials, in order to break through the UDC patent blockade on heavy metal phosphorescent complexes, and greatly To reduce costs.
  • the light-emitting materials provided by the present invention are used to prepare a series of high-performance TADF organic light-emitting diodes (OLED).
  • FIG. 1 is a flowchart of a method for preparing a thermally activated delayed fluorescence (TADF) material according to an embodiment of the present invention.
  • TADF thermally activated delayed fluorescence
  • Fig. 3 is a schematic diagram of the structure of an electroluminescent device according to an embodiment of the present invention.
  • the embodiment of the present invention provides a thermally activated delayed fluorescence (TADF) material, which serves as the main body of the green light-emitting guest, and utilizes the 100% internal quantum efficiency of the TADF material, so that the fluorescent device can reach the phosphorescent device (using phosphorescence).
  • TADF thermally activated delayed fluorescence
  • the efficiency of heavy metal complexes while solving the problems of excessively wide spectrum and long exciton lifetime, and overcoming the problem of poor color gamut of directly using TADF luminescent materials, in order to break through the UDC patent blockade on heavy metal phosphorescent complexes, and greatly To reduce costs.
  • the light-emitting materials provided by the present invention are used to prepare a series of high-performance TADF organic light-emitting diodes (OLED).
  • the present invention provides a thermally activated delayed fluorescence (TADF) material, which includes a compound composed of an acceptor A and a donor D, and the compound has the general structural formula shown in Formula 1:
  • TADF thermally activated delayed fluorescence
  • the receptor A is selected from any one of the following structural formulas:
  • the donor D is the following structural formula:
  • FIG. 1 is a flowchart of a method for preparing a thermally activated delayed fluorescence (TADF) material according to an embodiment of the present invention.
  • the present invention also provides a method for preparing a thermally activated delayed fluorescence (TADF) material, which includes the following steps:
  • Step S1 In an alkali-containing solution, the compound AX and the compound DH are reacted at a first temperature for a first period of time in the presence of a catalyst to obtain a reaction solution, wherein the X is a halogen, and the A is the following structural formula Either:
  • the D is the following structural formula:
  • Step S2 cooling the reaction liquid to a second temperature to obtain a mixture, wherein the molar ratio of the compound A-X to the compound D-H is 1:1;
  • Step S3 Separate the thermally activated delayed fluorescence (TADF) material from the mixture, including a compound composed of an acceptor A and a donor D, and the compound has the general structural formula shown in Formula 1:
  • TADF thermally activated delayed fluorescence
  • the first temperature is 80° C. to 150° C.
  • the first time period is 36 hours to 60 hours.
  • the second temperature is room temperature.
  • the solution in the preparation method of the thermally activated delayed fluorescence (TADF) material, in the step S1, the solution is toluene, and the alkali is sodium tert-butylate. , NaOtBu), and the catalyst includes palladium acetate and tri-tert-butylphosphine tetrafluoroborate.
  • the step S2 further includes extracting the reaction solution through dichloromethane several times and combining the organic phases to obtain the Said mixture.
  • the step S3 is to use column chromatography for separation, and the eluent used in the column chromatography Dichloromethane: n-hexane with a volume ratio of 1:1.
  • the step S1 is performed in an inert environment.
  • the present invention also provides an electroluminescent device, comprising: a base layer; a hole injection layer located on the base layer; a hole transport layer located on the hole injection layer; a light emitting layer located on the hole On the transport layer; the electron transport layer is located on the light-emitting layer; and the cathode layer is located on the electron transport layer, wherein the light-emitting layer includes the thermally activated delayed fluorescence (TADF) material provided by the present invention.
  • TADF thermally activated delayed fluorescence
  • the material of the base layer includes ITO;
  • the material of the hole injection layer includes 2,3,6,7,10,11-hexacyano -1,4,5,8,9,12-hexaazatriphenylene hexacarbonitrile (HATCN);
  • the material of the hole transport layer includes 4,4',4"-tris(carbazole-9- Base) triphenylamine (4,4',4"-Tris(carbazol-9-yl)-triphenylamine, TCTA);
  • the material of the electron transport layer includes 1,3,5-tris(3-(3-pyridyl) ) Phenyl) benzene (Tm3PyPB); and the material of the cathode layer includes lithium fluoride and aluminum.
  • the target thermally activated delayed fluorescence (TADF) material to be synthesized includes compound 1 of the following structural formula:
  • raw material 1 (1.75g, 5mmol), phenoxazine (1.10g, 6mmol), palladium acetate (45mg, 0.2mmol) and tri-tert-butylphosphine tetrafluoroborate (0.17g, 0.6mmol), and then add sodium tert-butylate (NaOtBu) (0.58g, 6mmol) in the glove box.
  • NaOtBu sodium tert-butylate
  • reaction solution was poured into 200 mL ice water, extracted with dichloromethane three times, and the organic phases were combined and separated and purified by silica gel column chromatography (dichloromethane: n-hexane, v: v, 1:1) to obtain 1.8 g of blue-white powder, with a yield of 79%.
  • the target thermally activated delayed fluorescence (TADF) material to be synthesized includes compound 2 of the following structural formula:
  • raw material 2 (1.75g, 5mmol), phenoxazine (1.10g, 6mmol), palladium acetate (45mg, 0.2mmol) and tri-tert-butylphosphine tetrafluoroborate (0.17g, 0.6 mmol), and then add sodium tert-butylate (NaOtBu) (0.58g, 6mmol) in the glove box, pour 40mL of toluene that has been dewatered and deoxygenated in an argon atmosphere, and react at 120°C for 48 hours .
  • NaOtBu sodium tert-butylate
  • the target thermally activated delayed fluorescence (TADF) material to be synthesized includes compound 3 of the following structural formula:
  • raw material 3 (1.75g, 5mmol), phenoxazine (1.10g, 6mmol), palladium acetate (45mg, 0.2mmol) and tri-tert-butylphosphine tetrafluoroborate (0.17g, 0.6 mmol), and then add sodium tert-butylate (NaOtBu) (0.58g, 6mmol) in the glove box, pour 40mL of toluene that has been dewatered and deoxygenated in an argon atmosphere, and react at 120°C for 48 hours .
  • NaOtBu sodium tert-butylate
  • reaction solution was poured into 200 mL ice water, extracted with dichloromethane three times, and the organic phases were combined and separated and purified by silica gel column chromatography (dichloromethane:n-hexane, v:v, 1:1) to obtain 1.0 g of blue-white powder, with a yield of 44%.
  • the compound 1, compound 2, and compound 3 were tested.
  • the fluorescence emission spectra of the compound 1, compound 2, and compound 3 under the pure film are shown in Fig. 2.
  • the compound 1, compound 2 , And compound 3 based on the B3LYP theory to calculate the lowest singlet (S1) and lowest triplet energy levels (T1), and detect HOMO as the highest occupied molecular orbital (Highest Occupied Molecular Orbital), and LUMO as the lowest unoccupied molecular orbital ( Lowest Unoccupied Molecular Orbital), the electrochemical energy obtained is shown in Table 1 below:
  • PL peak is the photoluminescence peak
  • S1 is the lowest singlet energy level
  • T 1 is the lowest triplet energy level
  • ⁇ E ST is the energy level difference between the lowest singlet energy level and the lowest triplet energy level
  • HOMO is the highest Occupied molecular orbital (Highest Occupied Molecular Orbital) energy pole
  • LUMO is the lowest unoccupied molecular orbital (Lowest Unoccupied Molecular Orbital) energy pole.
  • an embodiment of the present invention also provides an electroluminescent device including the above-mentioned thermally activated delayed fluorescence (TADF) material.
  • TADF thermally activated delayed fluorescence
  • the electroluminescent device 100 includes a base layer 1; a hole injection layer 2 located on the base layer 1; a hole transport layer 3 located on the hole injection layer 2
  • the light-emitting layer 4 is located on the hole transport layer 3; the electron transport layer 5 is located on the light-emitting layer 4; and the cathode layer 6 is located on the electron transport layer 5, wherein the light-emitting layer 4 includes the present
  • the invention provides a thermally activated delayed fluorescence (TADF) material.
  • TADF thermally activated delayed fluorescence
  • the material of the base layer 1 includes ITO; the material of the hole injection layer 2 includes 2, 3, 6, 7, 10, 11-6. Cyano-1,4,5,8,9,12-hexaazatriphenylene (HATCN); the material of the hole transport layer 3 includes 4,4',4"-tris(carbazole-9- Base) triphenylamine (4,4',4"-Tris(carbazol-9-yl)-triphenylamine, TCTA); the material of the electron transport layer 5 includes 1,3,5-tris(3-(3-pyridine) Phenyl)benzene (Tm3PyPB); and the material of the cathode layer 6 includes lithium fluoride and aluminum.
  • HTCN Cyano-1,4,5,8,9,12-hexaazatriphenylene
  • the material of the hole transport layer 3 includes 4,4',4"-tris(carbazole-9- Base) triphenylamine (4,4',4"-Tris(carbazol-9-yl)-triphenylamine
  • compound 1, compound 2, and compound 3 are used as the light-emitting layer 4 to fabricate the device 100, the device 200, and the device 300, and the performance of the device 100, the device 200, and the device 300 are measured.
  • the thickness of the base layer 1 and the hole injection layer 2 in the device 100, the device 200, and the device 300 is 2 nm.
  • the thickness of the hole transport layer 3 is 35 nm.
  • the light-emitting layer 4 of the device 100, the device 200, and the device 300 respectively includes 7% of Compound 1, Compound 2, and Compound 3, with a thickness of 40 nm.
  • the thickness of the electron transport layer 5 is 40 nm.
  • the thickness of lithium fluoride in the cathode 6 is 1 nm, and the thickness of aluminum is 100 nm.
  • the embodiment of the present invention provides a thermally activated delayed fluorescence (TADF) material, which serves as the main body of the green light-emitting guest, and uses the 100% internal quantum efficiency of the TADF material to enable the fluorescent device to be a phosphorescent device.
  • TADF thermally activated delayed fluorescence
  • the efficiency of (using phosphorescent heavy metal complexes) simultaneously solves the problems of excessively broad spectrum and long exciton lifetime, and overcomes the problem of the color gamut difference of directly using TADF luminescent materials to break through the UDC patent blockade on heavy metal phosphorescent complexes. And greatly reduce costs.
  • the light-emitting materials provided by the present invention are used to prepare a series of high-performance TADF organic light-emitting diodes (OLED).

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Abstract

本发明提供了一种热活化延迟荧光材料及其制备方法和电致发光器件，所述热活化延迟荧光(TADF)材料，包括由受体A及给体D所组成的化合物，所述化合物具有如式1所示的结构通式： D-A式1 其中所述受体A是择自下列结构式(A)中任一者：以及所述给体D是下列结构式(D)。

Description

热活化延迟荧光材料及其制备方法和电致发光器件 技术领域
本发明涉及显示技术领域，尤其涉及一种热活化延迟荧光(thermally activated delayed fluorescence，TADF)材料及其制备方法和电致发光器件。
背景技术
有机电致发光二极管(organic light-emitting diodes，OLED)显示装置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，柔性显示等优点以及巨大的应用前景，吸引了众多研究者的关注。
现有的OLED显示装置通常包括：基板、设于基板上的阳极、设于阳极上的有机发光层，设于有机发光层上的电子传输层、及设于电子传输层上的阴极。工作时向有机发光层发射来自阳极的空穴和来自阴极的电子，将这些电子和空穴组合产生激发性电子-空穴对，并将激发性电子-空穴对从受激态转换为基态实现发光。
在OLED中，起主导作用的发光客体材料至关重要。早期的OLED使用的发光客体材料为荧光材料，由于在OLED中单重态和三重态的激子比例为1:3，因此基于荧光材料的OLED的理论内量子效率(internal quantum  efficiency,IQE)只能达到25％，极大的限制了荧光电致发光器件的应用。重金属配合物磷光材料由于重原子的自旋轨道耦合作用，使得它能够同时利用单重态和三重态激子而实现100％的IQE。然而，通常使用的重金属都是Ir、Pt等贵重金属，成本很高，并且重金属配合物磷光发光材料在蓝光材料方面尚有待突破。
纯有机热活化延迟荧光(thermally activated delayed fluorescence，TADF)材料，通过巧妙的分子设计，使得分子具有较小的最低单三重能级差(ΔEST)，这样三重态激子可以通过反向系间窜越(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，也可以实现100％的IQE。
对于TADF材料，快速的反向系间窜越常数(reverse intersystem-crossing,kRISC)以及高的光致发光量子产率(photoluminescence quantum yield,PLQY)是制备高效率OLED的必要条件。目前，具备上述条件的TADF材料相对于重金属Ir配合物而言还是比较匮乏。由于TADF材料非常宽的光谱，以及微秒量级的激子寿命，极大地限制了其在量产器件结构中的应用。
技术问题
据此，亟需开发一种热活化延迟荧光(TADF)材料，作为绿光发光客体的主体，利用TADF材料100％的内量子效 率，使得荧光器件能够达到磷光器件的效率，同时解决了光谱过宽，激子寿命过长的问题，以突破UDC磷光重金属配合物专利封锁的有效路径。
技术解决方案
本发明的目的在于提供一种热活化延迟荧光(thermally activated delayed fluorescence，TADF)材料，作为绿光发光客体的主体，利用TADF材料100％的内量子效率，使得荧光器件能够达到磷光器件(使用磷光重金属配合物)的效率，同时解决了光谱过宽，激子寿命过长的问题，克服了直接使用TADF发光材料色域差的问题，以突破UDC关于重金属磷光配合物的专利封锁，并且大幅度地降低成本。利用本发明所提供的这些发光材料来制备一系列高性能的TADF有机发光二极管(organic light-emitting diodes，OLED)。
为实现上述目的，本发明提供了一种热活化延迟荧光(TADF)材料，包括由受体A及给体D所组成的化合物，所述化合物具有如式1所示的结构通式：
D-A 式1
其中所述受体A是择自下列结构式中任一者：
Figure PCTCN2020071737-appb-000001
；以及
所述给体D是下列结构式：
Figure PCTCN2020071737-appb-000002
本发明还提供了一种热活化延迟荧光(TADF)材料的制备方法，包括如下步骤：
步骤S1、在含碱的溶液中，使化合物A-X及化合物D-H在催化剂的存在下，于第一温度下反应第一时长以得到一反应液，其中所述X为卤素，所述A为下列结构式中任一者：
Figure PCTCN2020071737-appb-000003
；以及
所述D为下列结构式：
Figure PCTCN2020071737-appb-000004
步骤S2、将所述反应液冷却至第二温度，得到一混合物；以及
步骤S3、自所述混合物分离出所述热活化延迟荧光(TADF)材料，包括由受体A及给体D所组成之化合物，所述化合物具有如式1所示的结构通式：
D-A 式1。
依据本发明的一实施例，在所述的热活化延迟荧光(TADF)材料的制备方法中，所述第一温度为80℃至150℃，所述第一时长为36小时至60小时。
依据本发明的一实施例，在所述的热活化延迟荧光(TADF)材料的制备方法中，所述第二温度为室温。
依据本发明的一实施例，在所述的热活化延迟荧光(TADF)材料的制备方法中，所述步骤S1中，所述溶液为甲苯，所述碱为叔丁醇钠(sodium tert-butylate,NaOtBu)，且所述催化剂包括醋酸钯及三叔丁基膦四氟硼酸盐。
依据本发明的一实施例，在所述的热活化延迟荧光(TADF)材料的制备方法中，所述步骤S2更包括将所述反应液经过二氯甲烷萃取数次以及合并有机相以得到所述混合物。
依据本发明的一实施例，在所述的热活化延迟荧光(TADF)材料的制备方法中，所述步骤S3是使用管柱层析 进行分离，所述管柱层析所采用的淋洗液为体积比1:1的二氯甲烷:正己烷。
依据本发明的一实施例，所述步骤S1是在惰性环境下进行。
本发明又提供一种电致发光器件，包括：基底层；空穴注入层，位于所述基底层上；空穴传输层，位于所述空穴注入层上；发光层，位于所述空穴传输层上；电子传输层，位于所述发光层上；以及阴极层，位于所述电子传输层上，其中所述发光层包括本发明所提供的热活化延迟荧光(TADF)材料。
依据本发明的一实施例，在所述电致发光器件中，所述基底层的材料包括ITO；所述空穴注入层的材料包括2,3,6,7,10,11-六氰基-1,4,5,8,9,12-六氮杂苯并菲(hexaazatriphenylene hexacarbonitrile,HATCN)；所述空穴传输层的材料包括4,4',4”-三(咔唑-9-基)三苯胺(4,4',4”-Tris(carbazol-9-yl)-triphenylamine,TCTA)；所述电子传输层的材料包括1,3,5-三(3-(3-吡啶基)苯基)苯(Tm3PyPB)；以及所述阴极层的材料包括氟化锂及铝。
有益效果
本发明的目的在于提供一种热活化延迟荧光(thermally activated delayed fluorescence，TADF) 材料，作为绿光发光客体的主体，利用TADF材料100％的内量子效率，使得荧光器件能够达到磷光器件(使用磷光重金属配合物)的效率，同时解决了光谱过宽，激子寿命过长的问题，克服了直接使用TADF发光材料色域差的问题，以突破UDC关于重金属磷光配合物的专利封锁，并且大幅度地降低成本。利用本发明所提供的这些发光材料来制备一系列高性能的TADF有机发光二极管(organic light-emitting diodes，OLED)。
附图说明
为了更清楚地说明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单介绍，显而易见地，下面描述中的附图仅仅是发明的一些实施例，对于本领域普通技术人员来讲，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。
图1为本发明实施例的热活化延迟荧光(TADF)材料的制备方法的流程图。
图2为本发明的第一实施例及第二实施例中化合物1、化合物2及化合物3的荧光发射光谱图。
图3为本发明实施例的电致发光器件的结构示意图。
本发明的最佳实施方式
为让本发明的上述内容能更明显易懂，下文特举优选实施例，并配合所附图式作详细说明。
本发明实施例提供了一种热活化延迟荧光(thermally activated delayed fluorescence，TADF)材料，作为绿光发光客体的主体，利用TADF材料100％的内量子效率，使得荧光器件能够达到磷光器件(使用磷光重金属配合物)的效率，同时解决了光谱过宽，激子寿命过长的问题，克服了直接使用TADF发光材料色域差的问题，以突破UDC关于重金属磷光配合物的专利封锁，并且大幅度地降低成本。利用本发明所提供的这些发光材料来制备一系列高性能的TADF有机发光二极管(organic light-emitting diodes，OLED)。
为实现上述目的，本发明提供了一种热活化延迟荧光(TADF)材料，包括由受体A及给体D所组成的化合物，所述化合物具有如式1所示的结构通式：
D-A 式1
其中所述受体A是择自下列结构式中任一者：
Figure PCTCN2020071737-appb-000005
；以及
所述给体D是下列结构式：
Figure PCTCN2020071737-appb-000006
参见图1，图1为本发明实施例的热活化延迟荧光(TADF)材料的制备方法的流程图。如图1所示，本发明还提供了一种热活化延迟荧光(TADF)材料的制备方法，包括如下步骤：
步骤S1、在含碱的溶液中，使化合物A-X及化合物D-H在催化剂的存在下，于第一温度下反应第一时长以得到一反应液，其中所述X为卤素，所述A为下列结构式中任一者：
Figure PCTCN2020071737-appb-000007
；以及
所述D为下列结构式：
Figure PCTCN2020071737-appb-000008
步骤S2、将所述反应液冷却至第二温度，得到一混合物，其中所述化合物A-X与化合物D-H的莫尔比为1:1；以及
步骤S3、自所述混合物分离出所述热活化延迟荧光(TADF)材料，包括由受体A及给体D所组成之化合物，所述化合物具有如式1所示的结构通式：
D-A 式1。
依据本发明的一实施例，在所述的热活化延迟荧光(TADF)材料的制备方法中，所述第一温度为80℃至150℃，所述第一时长为36小时至60小时。
依据本发明的一实施例，在所述的热活化延迟荧光(TADF)材料的制备方法中，所述第二温度为室温。
依据本发明的一实施例，在所述的热活化延迟荧光(TADF)材料的制备方法中，所述步骤S1中，所述溶液为甲苯，所述碱为叔丁醇钠(sodium tert-butylate,NaOtBu)，且所述催化剂包括醋酸钯及三叔丁基膦四氟硼酸盐。
依据本发明的一实施例，在所述的热活化延迟荧光(TADF)材料的制备方法中，所述步骤S2更包括将所述反应液经过二氯甲烷萃取数次以及合并有机相以得到所述混合物。
依据本发明的一实施例，在所述的热活化延迟荧光 (TADF)材料的制备方法中，所述步骤S3是使用管柱层析进行分离，所述管柱层析所采用的淋洗液为体积比1:1的二氯甲烷:正己烷。
依据本发明的一实施例，所述步骤S1是在惰性环境下进行。
本发明又提供一种电致发光器件，包括：基底层；空穴注入层，位于所述基底层上；空穴传输层，位于所述空穴注入层上；发光层，位于所述空穴传输层上；电子传输层，位于所述发光层上；以及阴极层，位于所述电子传输层上，其中所述发光层包括本发明所提供的热活化延迟荧光(TADF)材料。
依据本发明的一实施例，在所述电致发光器件中，所述基底层的材料包括ITO；所述空穴注入层的材料包括2,3,6,7,10,11-六氰基-1,4,5,8,9,12-六氮杂苯并菲(hexaazatriphenylene hexacarbonitrile,HATCN)；所述空穴传输层的材料包括4,4',4”-三(咔唑-9-基)三苯胺(4,4',4”-Tris(carbazol-9-yl)-triphenylamine,TCTA)；所述电子传输层的材料包括1,3,5-三(3-(3-吡啶基)苯基)苯(Tm3PyPB)；以及所述阴极层的材料包括氟化锂及铝。
实施例1
在本发明的具体实施例1中，欲合成的目标热活化延迟荧光(TADF)材料包括下列结构式的化合物1：
Figure PCTCN2020071737-appb-000009
化合物1的合成路线如下反应式1所示：
Figure PCTCN2020071737-appb-000010
反应式1
化合物1的详细合成步骤如下：
.向100mL二口瓶中加入原料1(1.75g，5mmol)，吩恶嗪(1.10g，6mmol)，醋酸钯(45mg，0.2mmol)和三叔丁基膦四氟硼酸盐(0.17g，0.6mmol)，然后在手套箱中加入叔丁醇钠(sodium tert-butylate,NaOtBu)(0.58g，6mmol)，在氩气氛围下打入40mL事先除水除氧的甲苯，在120℃反应48小时。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，利用硅胶管柱层析(二氯甲烷:正己烷，v:v，1:1)进行分离纯化，得蓝白色粉末1.8g，产率79％。1H NMR(300MHz,CD2Cl2,δ):7.71(d,J＝7.2Hz,2H),7.14(d,J＝ 6.9Hz,2H),7.08(d,J＝6.6Hz,2H),7.06-6.93(m,6H).MS(EI)m/z:[M]+calcd for C25H12F5NO2,453.08；found,453.00.
实施例2
在本发明的具体实施例2中，欲合成的目标热活化延迟荧光(TADF)材料包括下列结构式的化合物2：
Figure PCTCN2020071737-appb-000011
化合物2的合成路线如下反应式2所示：
Figure PCTCN2020071737-appb-000012
反应式2
化合物2的详细合成步骤如下：
向100mL二口瓶中加入原料2(1.75g，5mmol)，吩恶嗪(1.10g，6mmol)，醋酸钯(45mg，0.2mmol)和三叔丁基膦四氟硼酸盐(0.17g，0.6mmol)，然后在手套箱中加入叔丁醇钠(sodium tert-butylate,NaOtBu)(0.58g，6mmol)，在氩气氛围下打入40mL事先除水除氧的甲苯，在120℃反应48小时。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，利用硅胶管柱层析(二氯甲烷:正己烷，v:v，1:1)进行分离纯化，得蓝白色粉末1.6g，产率70％。1H NMR(300MHz,CD2Cl2,δ):7.45(s,1H),7.40-7.27(m,3H),7.14(d,J＝6.6Hz,2H),7.06-6.93(m,6H).MS(EI)m/z:[M]+calcd for C25H12F5NO2,453.08；found,453.03。
实施例3
在本发明的具体实施例3中，欲合成的目标热活化延迟荧光(TADF)材料包括下列结构式的化合物3：
Figure PCTCN2020071737-appb-000013
化合物3的合成路线如下反应式3所示：
Figure PCTCN2020071737-appb-000014
反应式3
化合物3的详细合成步骤如下：
向100mL二口瓶中加入原料3(1.75g，5mmol)，吩恶嗪(1.10g，6mmol)，醋酸钯(45mg，0.2mmol)和三叔丁基膦四氟硼酸盐(0.17g，0.6mmol)，然后在 手套箱中加入叔丁醇钠(sodium tert-butylate,NaOtBu)(0.58g，6mmol)，在氩气氛围下打入40mL事先除水除氧的甲苯，在120℃反应48小时。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，利用硅胶管柱层析(二氯甲烷:正己烷，v:v，1:1)进行分离纯化，得蓝白色粉末1.0g，产率44％。1H NMR(300MHz,CD2Cl2,δ):7.70(d,J＝6.3Hz,1H),7.48(t,J＝6.9Hz,1H),7.28(t,J＝6.9Hz,1H),7.18(t,J＝7.2Hz,1H),7.14(d,J＝6.6Hz,2H),7.06-6.93(m,6H).MS(EI)m/z:[M]+calcd for C25H12F5NO2,453.08；found,453.01。
具体地，对所述化合物1、化合物2、及化合物3进行检验，所述化合物1、化合物2、及化合物3在纯膜下的荧光发射光谱如图2所示，所述化合物1、化合物2、及化合物3的基于B3LYP理论计算出最低单重态(S1)和最低三重态能级(T1)，并检测HOMO为最高占据分子轨道(Highest Occupied Molecular Orbital)，LUMO为最低未占分子轨道(Lowest Unoccupied Molecular Orbital)，所得电化学能极如下表1所示：
表1
Figure PCTCN2020071737-appb-000015
Figure PCTCN2020071737-appb-000016
其中，PL peak为光致发光峰，S1为最低单重态能级，T 1为最低三重态能级，ΔE ST为最低单重态能级与最低三重态能级的能级差，HOMO为最高占据分子轨道(Highest Occupied Molecular Orbital)能极，LUMO为最低未占分子轨道(Lowest Unoccupied Molecular Orbital)能极。
结合图2及表1可知，本发明的所述化合物1、化合物2、及化合物3的性能符合要求。
此外，本发明实施例还提供一种电致发光器件，包括上述的热活化延迟荧光(TADF)材料。
请参阅图3，具体而言，所述电致发光器件100包括基底层1；空穴注入层2，位于所述基底层1上；空穴传输层3，位于所述空穴注入层2上；发光层4，位于所述空穴传输层3上；电子传输层5，位于所述发光层4上；以及阴极层6，位于所述电子传输层5上，其中所述发光层4包括本发明所提供的热活化延迟荧光(TADF)材料。
依据本发明的一实施例，在所述电致发光器件中，所述基底层1的材料包括ITO；所述空穴注入层2的材料包 括2,3,6,7,10,11-六氰基-1,4,5,8,9,12-六氮杂苯并菲(HATCN)；所述空穴传输层3的材料包括4,4',4”-三(咔唑-9-基)三苯胺(4,4',4”-Tris(carbazol-9-yl)-triphenylamine,TCTA)；所述电子传输层5的材料包括1,3,5-三(3-(3-吡啶基)苯基)苯(Tm3PyPB)；以及所述阴极层6的材料包括氟化锂及铝。
具体地，分别采用化合物1、化合物2、及化合物3作为发光层4制作器件100、器件200、及器件300，并对所述器件100、器件200、及器件300进行性能进行测量。其中，所述器件100、器件200、及器件300中所述基底层1和所述空穴注入层2厚度为2nm。所述空穴传输层3的厚度为35nm。所述器件100、器件200、及器件300的发光层4分别包括7％的化合物1、化合物2、及化合物3，厚度为40nm。电子传输层5的厚度为40nm。阴极6中的氟化锂的厚度为1nm，铝的厚度为100nm。
进一步测量所述器件100、器件200、及器件300的电流-亮度-电压特性，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)所完成，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。测得的器件100、器件200、及器件 300的性能如表2所示，可知器件100、器件200、及器件300的性能符合要求。
表2
器件 最高电流效率(cd/A) CIEy 最大外量子效率(％)
器件100 86.7 0.25 34.1％
器件200 77.5 0.25 30.8％
器件300 64.3 0.25 28.9％
据此，本发明实施例提供了一种热活化延迟荧光(thermally activated delayed fluorescence，TADF)材料，作为绿光发光客体的主体，利用TADF材料100％的内量子效率，使得荧光器件能够达到磷光器件(使用磷光重金属配合物)的效率，同时解决了光谱过宽，激子寿命过长的问题，克服了直接使用TADF发光材料色域差的问题，以突破UDC关于重金属磷光配合物的专利封锁，并且大幅度地降低成本。利用本发明所提供的这些发光材料来制备一系列高性能的TADF有机发光二极管(organic light-emitting diodes，OLED)。
综上所述，虽然本发明已以优选实施例揭露如上，但上述优选实施例并非用以限制本发明，本领域的普通技术人员，在不脱离本发明的精神和范围内，均可作各种更动与润饰，因此本发明的保护范围以权利要求界定的范围为 准。

Claims (10)

  1. 一种热活化延迟荧光材料，包括由受体A及给体D所组成之化合物，所述化合物具有下列结构式：
    D-A式1
    其中所述受体A是择自下列结构式中任一者：
    Figure PCTCN2020071737-appb-100001
    ；以及
    所述给体D是下列结构式：
    Figure PCTCN2020071737-appb-100002
  2. 一种电致发光器件，包括：
    基底层；
    空穴注入层，位于所述基底层上；
    空穴传输层，位于所述空穴注入层上；
    发光层，位于所述空穴传输层上；
    电子传输层，位于所述发光层上；以及
    阴极层，位于所述电子传输层上，
    其中所述发光层包括如权利要求1所述的热活化延迟荧光材料。
  3. 如权利要求2所述的电致发光器件，其中
    所述基底层的材料包括ITO；
    所述注入层的材料包括2,3,6,7,10,11-六氰基-1,4,5,8,9,12-六氮杂苯并菲；
    所述空穴传输层的材料包括4,4',4”-三(咔唑-9-基)三苯胺；
    所述电子传输层的材料包括1,3,5-三(3-(3-吡啶基)苯基)苯(Tm3PyPB)；以及
    所述阴极层的材料包括氟化锂及铝。
  4. 一种热活化延迟荧光材料的制备方法，包括如下步骤：
    步骤S1、在含碱的溶液中，使化合物A-X及化合物D-H在催化剂的存在下，于第一温度下反应第一时长以得到反应液，其中所述X为卤素，所述A为下列结构式中任一者：
    Figure PCTCN2020071737-appb-100003
    ；以及
    所述D为下列结构式：
    Figure PCTCN2020071737-appb-100004
    步骤S2、将所述反应液冷却至第二温度，得到混合物；以及
    步骤S3、自所述混合物分离出所述热活化延迟荧光材料，包括由受体A及给体D所组成之化合物，所述化合物具有如式1所示的结构通式：
    D-A式1。
  5. 如权利要求4所述的热活化延迟荧光材料的制备方法，其中，所述第一温度为120℃，所述第一时长为48小时。
  6. 如权利要求4所述的热活化延迟荧光材料的制备方法，其中，所述第二温度为室温。
  7. 如权利要求4所述的热活化延迟荧光材料的制备方法，其中，所述步骤S1中，所述含碱的溶液为甲苯，所述碱为叔丁醇钠，且所述催化剂包括醋酸钯及三叔丁基膦四氟硼酸盐。
  8. 如权利要求4所述的热活化延迟荧光材料的制备方法，其中，所述步骤S2更包括将所述反应液经过二氯甲烷萃取数次以及合并有机相以得到所述混合物。
  9. 如权利要求4所述的热活化延迟荧光材料的制备 方法，其中，所述步骤S3是使用管柱层析进行分离，所述管柱层析所采用的淋洗液为体积比1:1的二氯甲烷:正己烷。
  10. 如权利要求4所述的热活化延迟荧光材料的制备方法，其中所述步骤S1是在惰性环境下进行。
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