WO2020220414A1 - 热活化延迟荧光材料及其制备方法、显示装置 - Google Patents

热活化延迟荧光材料及其制备方法、显示装置 Download PDF

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WO2020220414A1
WO2020220414A1 PCT/CN2019/088078 CN2019088078W WO2020220414A1 WO 2020220414 A1 WO2020220414 A1 WO 2020220414A1 CN 2019088078 W CN2019088078 W CN 2019088078W WO 2020220414 A1 WO2020220414 A1 WO 2020220414A1
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thermally activated
activated delayed
fluorescent material
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王彦杰
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Wuhan China Star Optoelectronics Semiconductor Display Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D223/00—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom
    • C07D223/14—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D223/18—Dibenzazepines; Hydrogenated dibenzazepines
    • C07D223/22—Dibenz [b, f] azepines; Hydrogenated dibenz [b, f] azepines
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    • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
    • C09K11/06—Luminescent materials, e.g. electroluminescent or chemiluminescent containing organic luminescent materials
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    • 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
    • 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
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems
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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
    • 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

Definitions

  • the invention relates to the technical field of organic electroluminescent materials, in particular to a thermally activated delayed fluorescent material, a preparation method thereof, and a display device.
  • Organic electroluminescence is a kind of luminescence phenomenon realized by the use of organic materials under the excitation of external electric field and current.
  • the layered OLED (Organic Light-Emitting Diode, organic light-emitting diode) structure has achieved higher brightness, higher external quantum efficiency and lower driving voltage, which has stimulated great interest in the research of OLED by scientific researchers. It is possible to realize commercialization.
  • OLED In recent years, due to its active light emission, large viewing angle, fast corresponding speed, wide temperature adaptation range, low driving voltage, low power consumption, high brightness, simple production process, light and thin, and flexible display, OLED displays And the lighting field shows great application prospects, attracting the attention of scientific researchers and companies.
  • 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.
  • Adachi et al. proposed a pure organic light-emitting molecule with a "Thermally Activated Delayed Fluorescence" (TADF) mechanism.
  • TADF Thermally Activated Delayed Fluorescence
  • the molecule has a smaller minimum singlet state and triplet energy.
  • Level difference ( ⁇ EST) so that the triplet excitons can return to the singlet state through RISC, and then radiate to the ground state to emit light, so that single and triplet excitons can be used at the same time to realize excitons
  • the utilization rate of 100% without the participation of heavy metals.
  • the TADF material has a rich structure design, and most of its physical properties are easily adjusted to obtain high-efficiency and long-life organic light-emitting materials that meet the requirements.
  • the ⁇ - ⁇ stacking between molecules is serious, and the ⁇ - ⁇ stacking easily causes the material to aggregate, leading to luminescence quenching.
  • the usual solution is to suppress the aggregation of materials to quench the luminescence phenomenon by doping.
  • the phenomenon of aggregation and quenching still exists after the general molecular doping, and the doping ratio of the luminescent material is small, which will reduce the efficiency of the device. .
  • the purpose of the present invention is to provide a thermally activated delayed fluorescent material, a preparation method thereof, and a display device to solve the problem of serious accumulation of ⁇ - ⁇ between molecules in the thermally activated delayed fluorescent material in the prior art, and electron acceptor and electron donor
  • HOMO Occupied Molecular Orbital
  • LUMO Lowest Unoccupied Molecular Orbital
  • the present invention provides a thermally activated delayed fluorescent material, which includes an electron donor and an electron acceptor.
  • the electron donor includes at least two benzene rings and a seven-membered ring connected between the two benzene rings.
  • the molecular structure of the electron donor includes one of the following structures:
  • the molecular structure of the electron acceptor includes one of the following structures:
  • the present invention also provides a method for preparing thermally activated delayed fluorescent material, which includes the following steps:
  • Synthesis of the first target placing the electron donor, the electron acceptor, and the catalyst in a reaction vessel to obtain a reaction solution, fully reacting in an argon atmosphere to obtain a mixed solution, and the mixed solution contains the target produced by the reaction.
  • Extracting the first target cooling the mixed solution to room temperature, and extracting the target in the mixed solution.
  • Purifying the first target purifying the target to obtain the near-infrared photothermal activated delayed fluorescent material.
  • the catalyst is toluene, potassium carbonate and palladium tetrakistriphenylphosphine.
  • the electron acceptor, the electron donor, the toluene and the potassium carbonate are placed together in the reaction vessel, and then the reaction vessel is placed in an argon atmosphere, and the reaction vessel is added The palladium tetrakistriphenylphosphorus is used to obtain a reaction solution.
  • the step of extracting the target substance includes adding dichloromethane to the reaction solution for extraction, and drying after multiple extractions to obtain the target substance.
  • the step of purifying and treating the target substance includes using an eluent to purify the target substance for the first time by a silica gel column chromatography method to obtain the thermally activated delayed fluorescence material.
  • the eluent in the silica gel column chromatography method is petroleum ether and dichloromethane, and the volume ratio of the petroleum ether and the dichloromethane is 1:1.
  • the step of synthesizing the first target it further includes a step of forming an electron donor.
  • the step of forming an electron donor includes the following steps:
  • Synthesis of the second target placing the first compound, the second compound and the catalyst in a reaction vessel to obtain a reaction solution, and fully react in an argon atmosphere to obtain a mixed solution, and the mixed solution contains the target produced by the reaction.
  • Extracting the second target cooling the mixed solution to room temperature, and extracting the target in the mixed solution.
  • Purifying the second target purifying the target to obtain a third compound having the electron donor structure.
  • the structure of the first compound has at least two benzene rings and a seven-membered ring connected between the two benzene rings.
  • the second compound has at least one benzene ring in its structure.
  • the catalyst is tris(dibenzylideneacetone) dipalladium, tri-tert-butylphosphine ⁇ tetrafluoroborate, sodium tert-butoxide and toluene.
  • the present invention also provides a display device, which includes a substrate, a first electrode layer, an injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and a second electrode layer.
  • the first electrode layer is provided on the substrate.
  • the injection layer is provided on the first electrode layer.
  • the hole transport layer is provided on the injection layer.
  • the light-emitting layer is provided on the hole transport layer.
  • the electron transport layer is provided on the light-emitting layer.
  • the second electrode layer is provided on the electron transport layer.
  • the light-emitting layer includes the thermally activated delayed fluorescent material as described above.
  • the material of the injection layer is 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene.
  • the material of the hole transport layer is 4,4'-cyclohexylbis[N,N-bis(4-methylphenyl)aniline]. Therefore, the material of the electron transport layer is 1,3,5-tris(3-(3-pyridyl)phenyl)benzene.
  • the advantages of the present invention are: a thermally activated delayed fluorescent material in the present invention, the two benzene rings in its molecular structure are connected by a saturated seven-membered ring, which can effectively inhibit the ⁇ - ⁇ stacking between molecules, thereby obtaining high Photoluminescence quantum efficiency (PLQY), and its electron donating ability is between diphenylamine and acridine, which can effectively reduce the overlap of HOMO and LUMO between the electron acceptor and the electron donor, and obtain the lowest singlet and
  • the thermally activated delayed fluorescent material with a small triple energy level difference greatly reduces the phenomenon of luminescence quenching and improves the working efficiency of the display device.
  • the preparation method of the thermally activated delayed fluorescent material in the present invention has simple process, easy purification and high yield.
  • the light-emitting layer contains the thermally activated delayed fluorescent material, so that the fluorescent efficiency of the light-emitting layer is higher and the stability is better, thereby also improving the luminous efficiency and service life of the display device.
  • Fig. 1 is a preparation process of thermally activated delayed fluorescent material in an embodiment of the present invention
  • Figure 2 is a preparation process of the step of forming an electron donor in an embodiment of the present invention
  • Figure 3 is a fluorescence emission spectrum of a thermally activated delayed fluorescent material in an embodiment of the present invention.
  • FIG. 4 is a layered structure diagram of a display device in an embodiment of the present invention.
  • Injection layer 103 Hole transport layer 104;
  • Electron transport layer 106 Light emitting layer 105; Electron transport layer 106;
  • the second electrode layer 107 The second electrode layer 107.
  • the molecular structure of the thermally activated delayed fluorescent material provided in the embodiment of the present invention is a D-A structure formed by the reaction of an electron donor (D) and an electron acceptor (A).
  • the molecular structure of the electron donor (D) includes at least two benzene rings and a seven-membered ring connected between the two benzene rings, and its molecular structure includes one of the following structures:
  • the molecular structure of the electron acceptor (A) includes one of the following structures:
  • thermoly activated delayed fluorescent materials of DA structure can be combined, and the thermally activated delayed fluorescent materials are used as luminescent guests.
  • organic electroluminescent devices organic electroluminescent devices with higher efficiency and performance can be prepared.
  • the embodiment of the present invention also provides a method for preparing the thermally activated delayed fluorescent material.
  • the compound with the electron donor (D) is 5-(4-bromophenyl)-5H-dibenzo[b,f]cycloheximide, which has the electron acceptor
  • the compound of (A) is 2-(4,4,5,5-tetramethyl-1,3,2-1,3,2-dioxoborolan-2-yl)-anthraquinone, the The molecular structural formula of the target thermally activated delayed fluorescent material prepared by the preparation method is:
  • the thermally activated delayed fluorescent material of this molecular structure is one of the above 24 kinds of thermally activated delayed fluorescent materials of D-A structure.
  • the preparation process is shown in Figure 1, and the specific preparation steps are as follows:
  • Step S10) Forming an electron donor (D):
  • the first compound iminodibenzyl and the second compound p-bromoiodobenzene react under the action of a catalyst to synthesize the compound 5-(4-bromo) having an electron donor (D) Phenyl)-5H-dibenzo[b,f]cycloheximine.
  • Step S20 Synthesis of the first target: in a 250mL three-necked flask, add 5-(4-bromophenyl)-5H-dibenzo[b,f]cyclohexanimine (3.49g, 10mmol), 2 -(4,4,5,5-tetramethyl-1,3,2-1,3,2-dioxoborolan-2-yl)-anthraquinone (3.34g, 10mmol), 50mL of toluene And 20mL of 2.5M potassium carbonate aqueous solution, and use argon for pumping.
  • 5-(4-bromophenyl)-5H-dibenzo[b,f]cyclohexanimine 3.49g, 10mmol
  • 2 -(4,4,5,5-tetramethyl-1,3,2-1,3,2-dioxoborolan-2-yl)-anthraquinone 3.34g, 10mmol
  • Step S30) Extract the first target; after the mixed solution is cooled to room temperature, it is extracted three times with dichloromethane and washed three times with water, and then the extract obtained after three extractions is dried and filtered with anhydrous sodium sulfate and spin-dried to obtain The first target.
  • Step S40 Purify the first target; use 200-300 mesh silica gel column chromatography, and use petroleum ether and dichloromethane (volume ratio of 1:1) as eluents to separate and purify the product, and finally obtain 4.05 g
  • the delayed fluorescent material is thermally activated, and the yield is 85%.
  • the compound with the electron donor (D) used is 5-(4-bromophenyl)-5H-dibenzo[b,f]cycloheximine, which has an electron acceptor
  • the compound of body (A) is 2-(4,4,5,5-tetramethyl-1,3,2-1,3,2-dioxoborolan-2-yl)-anthraquinone, but It is not limited to these two compounds. In other embodiments of the present invention, it can also be other compounds, but the preparation methods are basically the same, so they are not listed here.
  • the first compound and the second compound are reacted to synthesize a compound with an electron donor (D) under the action of a catalyst.
  • the preparation process of the step of forming an electron donor is as follows As shown in Figure 2, the specific preparation steps are as follows:
  • Step S11) Synthesis of the second target: In a 100mL Schlenk bottle, add iminodibenzyl (1.95g, 10mmol), p-bromoiodobenzene (4.24g, 10mmol), tris(dibenzylidene) Acetone) two palladium (0.18g, 0.2mmol), tri-tert-butylphosphine ⁇ tetrafluoroborate (0.23g, 0.8mmol) and sodium tert-butoxide (2.40g, 25mmol), then use argon for pumping , And adding 40 mL of anhydrous and oxygen-free toluene, the reaction solution is fully reacted in an argon atmosphere to obtain a mixed solution, and the mixed solution contains the second target produced by the reaction.
  • Step S12) Extract the second target; after the mixed solution is cooled to room temperature, it is extracted three times with dichloromethane and washed three times with water, and then the extract obtained after three extractions is dried, filtered and concentrated with anhydrous sodium sulfate to obtain the second Two target objects.
  • Step S13) Purify the second target; use 200-300 mesh silica gel column chromatography, and use petroleum ether and dichloromethane (volume ratio 1:1) as eluents to separate and purify the product to obtain 3.22 g
  • the compound 5-(4-bromophenyl)-5H-dibenzo[b,f]cycloheximine of the electron donor (D) has a yield of 92%.
  • the first compound is iminodibenzyl
  • the second compound is p-bromoiodobenzene, but it is not limited to these two compounds. In other embodiments of the present invention, it can be used as required. Adjusted to other compounds, but the preparation method is basically the same, so I won't list them all here.
  • the fluorescence emission spectrum of the thermally activated delayed fluorescent material prepared in the embodiment of the present invention is shown in FIG. 3. It is based on the calculated photoluminescence peak (PL Peak), lowest singlet state (S 1 ), lowest triplet energy level (T 1 ), lowest singlet and triplet energy level difference ( ⁇ EST), and photoluminescence peak calculated based on the B3LYP theory.
  • Luminous quantum efficiency (PLQY) is shown in Table 1:
  • the two benzene rings in the molecular structure are connected by a saturated seven-membered ring, which can effectively inhibit the ⁇ - ⁇ stacking between molecules, thereby obtaining high photoinduced Luminous quantum efficiency (PLQY), and its electron donating ability is between diphenylamine and acridine, which can effectively reduce the overlap of HOMO and LUMO between the electron acceptor and the electron donor, and obtain the lowest singlet and triplet energy
  • PLQY photoinduced Luminous quantum efficiency
  • acridine is between diphenylamine and acridine, which can effectively reduce the overlap of HOMO and LUMO between the electron acceptor and the electron donor, and obtain the lowest singlet and triplet energy
  • the thermally activated delayed fluorescent material with a small level difference greatly reduces the phenomenon of luminescence quenching and improves the working efficiency of the display device.
  • the method for preparing a thermally activated delayed fluorescent material provided in the embodiment of the present invention has a simple process, easy purification and high yield.
  • An embodiment of the present invention also provides a display device.
  • the display device includes a substrate 101, a first electrode layer 102, an injection layer 103, a hole transport layer 104, and a light emitting layer 105. , An electron transport layer 106 and a second electrode layer 107.
  • the substrate 101 is a glass substrate for protecting the overall structure of the display device 100.
  • the first electrode layer 102 is disposed on the substrate 101, and is made of indium tin oxide transparent conductive glass for transmitting current.
  • the injection layer 103 is disposed on the first electrode layer 102, and its material is 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaaza Triphenylene (HATCH) is used to effectively inject hole energy from the first electrode layer 102 into the device.
  • HATCH 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaaza Triphenylene
  • the hole transport layer 104 is provided on the injection layer 103, and its material is 4,4'-cyclohexylbis[N,N-bis(4-methylphenyl)aniline] (TAPC), which is used to The holes injected from the electrode are transported to the light-emitting layer 105.
  • the light-emitting layer 105 is disposed on the hole transport layer 104, and its material includes the thermally activated delayed fluorescent material, which converts electrical energy into light energy, thereby providing a light source for the display device 100.
  • the electron transport layer 106 is provided on the light-emitting layer 105, and its material is 1,3,5-tris(3-(3-pyridyl)phenyl)benzene (Tm3PyPB) for electrons injected from the electrode To the light-emitting layer 105.
  • the second electrode layer 107 is disposed on the electron transport layer 106, and its material is lithium fluoride or aluminum.
  • the applied voltage energy will drive electrons and holes to be injected into the light-emitting layer 104 from the hole transport layer 103 and the electron transport layer 105 respectively, and in the When the light-emitting layer 104 meets and combines, the so-called electron-hole recombination is formed.
  • a chemical molecule is excited by external energy, if the electron spin is paired with the ground state electron, it is a singlet state, and the light released is so-called fluorescence. Conversely, if the spins of the excited state electrons and the ground state electrons are not paired and parallel, it is called a triplet state, and the light emitted is so-called phosphorescence.
  • a performance test was performed on the final product display device 100 containing the thermally activated delayed fluorescent material. This test mainly detects the highest brightness, electroluminescence peak (EL Peak) and the maximum external quantum efficiency. The specific data is shown in Table 2.
  • the current, brightness, and voltage characteristics of the device are completed by the Keithley source measurement system (Keithley 2400 Sourcemeter, Keithley 2000 Currentmeter) with a calibrated silicon photodiode, and the electroluminescence spectrum is measured by the French JY company SPEX CCD3000 spectrometer Yes, all measurements are done in room temperature atmosphere.
  • the Keithley source measurement system Kelvin 2400 Sourcemeter, Keithley 2000 Currentmeter
  • the electroluminescence spectrum is measured by the French JY company SPEX CCD3000 spectrometer Yes, all measurements are done in room temperature atmosphere.
  • the near-infrared photothermally activated delayed fluorescent material of the present invention has excellent light-emitting performance, and the light-emitting layer 105 made of it has higher fluorescent efficiency and better stability, thereby also improving the light-emitting efficiency of the display device 100 and Service life.
  • the light-emitting layer of the display device contains the thermally activated delayed fluorescent material, so that the fluorescent efficiency of the light-emitting layer is higher, and the stability is better, thereby also improving the display device The luminous efficiency and service life.

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Abstract

提供了一种热活化延迟荧光材料及其制备方法、显示装置，所述热活化延迟荧光材料中包括电子给体与电子受体。其中，所述电子给体中包括至少两个苯环以及连接在两个苯环之间的七元环。所述制备方法工艺简单，纯化容易，产率高。所述显示装置中的发光层包含所述热活化延迟荧光材料。

Description

热活化延迟荧光材料及其制备方法、显示装置 技术领域
本发明涉及有机电致发光材料技术领域，特别是一种热活化延迟荧光材料及其制备方法、显示装置。
背景技术
有机电致发光是利用有机材料在外加电场和电流的激发作用下而实现的一种发光现象。
1963年美国纽约大学的Pope等人就首先以单晶蒽为发光层在100V的驱动电压下观察到了有机电致发光现象，但是由于发光效率低，驱动电压过高等缺陷使得其并未引起广泛的关注。直到1987年，由美国柯达公司的C.W.Tang等人采用真空蒸镀技术，以芳香二胺为空穴传输层，8-羟基喹啉铝(Alq3)为电子传输层和发光层所制备的新型多层OLED(Organic Light-Emitting Diode，有机发光二极管)结构获得了较高的亮度，较高的外量子效率以及较低的驱动电压，激发了科研工作者对OLED研究的极大兴趣，也为其能够实现商业化提供了可能。
近年来，OLED由于其主动发光、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。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铱(Ir)、铂(Pt)、锇(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”(Thermally Activated Delayed Fluorescence，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，特别是红光材料，由于含有大平面的受体结构，分子之间的π-π堆积严重，而π-π堆积容易造成材料聚集，导致发光淬灭。通常的解决办法都是通过掺杂的方式来抑制材料的聚集淬灭发光现象，但是一般的分子掺杂后依然存在聚集淬灭现象，并且发光材料的掺杂比例小时，会导致器件的效率降低。
技术问题
本发明的目的是提供一种热活化延迟荧光材料及其制备方法、显示装置，以解决现有技术中热活化延迟荧光材料中分子之间的π-π堆积严重，电子受体和电子给体之间的最高占有分子轨道(Highest Occupied Molecular Orbital，HOMO)和最低占有分子轨道(Lowest Unoccupied Molecular Orbital，LUMO)的重叠程度高，最低单重态和三重能级差过大，从而导致的发光淬灭现象，显示器件的工作效率较低等问题。
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，所述热活化延迟荧光材料中包括电子给体与电子受体。其中，所述电子给体中包括至少两个苯环以及连接在两个苯环之间的七元环。
进一步地，所述电子给体的分子结构中包括以下结构中的一种：
Figure PCTCN2019088078-appb-000001
进一步地，所述电子受体的分子结构中包括以下结构中的一种：
Figure PCTCN2019088078-appb-000002
本发明中还提供一种热活化延迟荧光材料的制备方法，包括以下步骤：
合成第一目标物：将电子给体、电子受体以及催化剂置于反应容器中，得到反应液，在氩气环境下充分反应得到混合溶液，所述混合溶液中具有反应生成的目标物。
萃取第一目标物：将所述混合溶液冷却至室温，萃取所述混合溶液中的所述目标物。
纯化处理第一目标物：对所述目标物进行纯化处理，得到所述近红外光热激活延迟荧光材料。
进一步地，所述合成第一目标物步骤中，所述催化剂为甲苯、碳酸钾和四三苯基膦钯。所述电子受体、所述电子给体、所述甲苯和所述碳酸钾一起放置于所述反应容器中，再将所述反应容器放置于氩气环境中，并往所述反应容器中加入所述四三苯基磷钯，得到反应液。
进一步地，所述萃取目标物步骤中包括将反应液中加入二氯甲烷进行萃取，多次萃取后进行干燥，得到所述目标物。
进一步地，所述纯化处理目标物步骤中包括使用淋洗液，通过硅胶柱层析方法进行初次纯化所述目标物，得到所述热活化延迟荧光材料。其中，所述硅胶柱层析方法中的淋洗液为石油醚和二氯甲烷，所述石油醚和所述二氯甲烷的体积比为1:1。
进一步地，在所述合成第一目标物步骤前还包括形成电子给体步骤。所述形成电子给体步骤包括以下步骤：
合成第二目标物：将第一化合物、第二化合物以及催化剂置于反应容器中，得到反应液，在氩气环境下充分反应得到混合溶液，所述混合溶液中具有反应生成的目标物。
萃取第二目标物：将所述混合溶液冷却至室温，萃取所述混合溶液中的所述目标物。
纯化处理第二目标物：对所述目标物进行纯化处理，得到具有所述电子给体结构的第三化合物。
其中，所述第一化合物的结构中具有至少两个苯环以及连接在两个苯环之间的七元环。所述第二化合物的结构中具有至少一个苯环。
进一步地，所述催化剂为三(二亚苄基丙酮)二钯、三叔丁基膦·四氟硼酸盐、叔丁醇钠和甲苯。
本发明中还提供一种显示装置，所述显示装置包括一基板、一第一电极层、一注入层、一空穴传输层、一发光层、一电子传输层以及一第二电极层。所述第一电极层设于所述基板上。所述注入层设于所述第一电极层上。所述空穴传输层设于所述注入层上。所述发光层设于所述空穴传输层上。所述电子传输层设于所述发光层上。所述第二电极层设于所述电子传输层上。其中，所述发光层包括如上所述的热活化延迟荧光材料。
进一步地，所述注入层的材料为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为4,4'-环己基二[N,N-二(4-甲基苯基)苯胺]。所以电子传输层的材料为1,3,5-三(3-(3-吡啶基)苯基)苯。
有益效果
本发明的优点是：本发明中的一种热活化延迟荧光材料，其分子结构中的两个苯环通过饱和七元环进行连接，能够有效抑制分子间的π-π堆积，从而获得高的光致发光量子效率(PLQY)，并且其给电子能力介于二苯胺和吖啶之间，能够有效减低电子受体和电子给体之间的HOMO和LUMO的重叠程度，获得最低单重态和三重能级差较小的热活化延迟荧光材料，从而大大减少了发光淬灭现象，提高了显示器件的工作效率。
本发明中一种热活化延迟荧光材料制备方法，其工艺简单，纯化容易，产率高。
本发明中一种显示装置，其发光层包含所述热活化延迟荧光材料，使发光层的荧光效率更高，稳定性更好，从而也提高了显示装置的发光效率以及使用寿命。
附图说明
图1为本发明实施例中热活化延迟荧光材料的制备流程；
图2本发明实施例中形成电子给体步骤的制备流程；
图3为本发明实施例中热活化延迟荧光材料的荧光发射光谱；
图4为本发明实施例中显示装置的层状结构图。
图中部件表示如下：
显示装置    100；
基板        101；   第一电极层  102；
注入层      103；   空穴传输层  104；
发光层      105；   电子传输层  106；
第二电极层  107。
本发明的实施方式
以下结合说明书附图详细说明本发明的优选实施例，以向本领域中的技术人员完整介绍本发明的技术内容，以举例证明本发明可以实施，使得本发明公开的技术内容更加清楚，使得本领域的技术人员更容易理解如何实施本发明。然而本发明可以通过许多不同形式的实施例来得以体现，本发明的保护范围并非仅限于文中提到的实施例，下文实施例的说明并非用来限制本发明的范围。
本发明的说明书和权利要求书以及上述附图中的术语“第一”、“第二”、“第三”等(如果存在)是用于区别类似的对象，而不必用于描述特定的顺序或先后次序。应当理解，这样描述的对象在适当情况下可以互换。
本发明说明书中使用的术语仅用来描述特定实施方式，而并不意图显示本发明的概念。除非上下文中有明确不同的意义，否则，以单数形式使用的表达涵盖复数形式的表达。在本发明说明书中，应理解，诸如“包括”、“具有”以及“含有”等术语意图说明存在本发明说明书中揭示的特征、数字、步骤、动作或其组合的可能性，而并不意图排除可存在或可添加一个或多个其他特征、数字、步骤、动作或其组合的可能性。
上下文有明确的相反提示，否则本文中所述的所有方法的步骤都可以按任何适当次序加以执行。本发明的改变并不限于描述的步骤顺序。除非另外主张，否则使用本文中所提供的任何以及所有实例或示例性语言(例如，“例如”)都仅仅为了更好地说明本发明的概念，而并非对本发明的概念的范围加以限制。在不脱离精神和范围的情况下，所属领域的技术人员将易于明白多种修改和适应。
本发明实施例中提供的热活化延迟荧光材料的分子结构为电子给体(D)和电子受体(A)反应生成的D-A结构。其中，所述电子给体(D)的分子结构中包括至少两个苯环以及连接在两个苯环之间的七元环，其分子结构中包括以下结构中的一种：
Figure PCTCN2019088078-appb-000003
所述电子受体(A)的分子结构中包括以下结构中的一种：
Figure PCTCN2019088078-appb-000004
通过以上包括以上所述结构的电子给体(D)和电子受体(A)的排列组合，一共能够组合出24种D-A结构的热活化延迟荧光材料，所述热活化延迟荧光材作为发光客体应用于有机电致发光器件中，能够制备出更加高效率高性能的有机电致发光器件。
本发明实施例中还提供一种热活化延迟荧光材料的制备方法。在本实施例中，具有所述电子给体(D)的化合物为5-(4-溴代苯基)-5H-二苯并[b,f]环己亚胺，具有所述电子受体(A)的化合物为2-(4,4,5,5-四甲基-1,3,2-1,3,2-二氧代硼戊环-2-基)-蒽醌，所述制备方法制备的目标热活化延迟荧光材料的分子结构式为：
Figure PCTCN2019088078-appb-000005
此分子结构的热活化延迟荧光材料为上述24种D-A结构的热活化延迟荧光材料中一种。其制备流程如图1所示，具体制备步骤如下：
步骤S10)形成电子给体(D)：通过第一化合物亚氨基二苄和第二化合物对溴碘苯在催化剂的作用下反应合成具有电子给体(D)的化合物5-(4-溴代苯基)-5H-二苯并[b,f]环己亚胺。
步骤S20)合成第一目标物：在250mL的三口瓶中，加入5-(4-溴代苯基)-5H-二苯并[b,f]环己亚胺(3.49g，10mmol)、2-(4,4,5,5-四甲基-1,3,2-1,3,2-二氧代硼戊环-2-基)-蒽醌(3.34g，10mmol)、50mL的甲苯和20mL的2.5M碳酸钾水溶液，并使用氩气进行抽换气。然后加入四三苯基磷钯(0.72g，0.6mmol)，反应液在氩气的环境下充分反应得到混合溶液，所述混合溶液中具有反应生成的第一目标物。
步骤S30)萃取第一目标物；将混合溶液冷却至室温后，使用二氯甲烷萃取三次，并水洗三次，然后将三次萃取后所得的萃取物使用无水硫酸钠进行干燥过滤并旋干，得到第一目标物。
步骤S40)纯化处理第一目标物；使用200-300目的硅胶柱层析，并用石油醚和二氯甲烷(体积比为1:1)作为淋洗剂，对产物进行分离纯化，最后得到4.05g热活化延迟荧光材料，产率85％。
其制备流程如式1所示：
Figure PCTCN2019088078-appb-000006
在本实施例中，使用到的具有所述电子给体(D)的化合物为5-(4-溴代苯基)-5H-二苯并[b,f]环己亚胺，具有电子受体(A)的化合物为2-(4,4,5,5-四甲基-1,3,2-1,3,2-二氧代硼戊环-2-基)-蒽醌，但并不仅限于这两种化合物，在本发明的其他实施例中，还可以为其他化合物，但制备方法基本相同，在此不一一列举。
所述形成电子给体(D)步骤通过所述第一化合物和所述第二化合物在催化剂的作用下反应合成具有电子给体(D)的化合物，所述形成电子给体步骤的制备流程如图2所示，具体制备步骤如下：
步骤S11)合成第二目标物：在100mL的施兰克(schlenk)瓶中，加入亚氨基二苄(1.95g，10mmol)、对溴碘苯(4.24g，10mmol)、三(二亚苄基丙酮)二钯(0.18g，0.2mmol)、三叔丁基膦·四氟硼酸盐(0.23g，0.8mmol)和叔丁醇钠(2.40g，25mmol)，然后使用氩气进行抽换气，并加入40mL无水无氧的甲苯，反应液在氩气的环境下充分反应得到混合溶液，所述混合溶液中具有反应生成的第二目标物。
步骤S12)萃取第二目标物；将混合溶液冷却至室温后，使用二氯甲烷萃取三次，并水洗三次，然后将三次萃取后所得的萃取物使用无水硫酸钠进行干燥过滤并浓缩，得到第二目标物。
步骤S13)纯化处理第二目标物；使用200-300目的硅胶柱层析，并用石油醚和二氯甲烷(体积比为1:1)作为淋洗剂，对产物进行分离纯化，得到3.22g具有所述电子给体(D)的化合物5-(4-溴代苯基)-5H-二苯并[b,f]环己亚胺，产率92％。
其制备流程式如式2所示：
Figure PCTCN2019088078-appb-000007
在本实施例中，所述第一化合物为亚氨基二苄，所述第二化合物为对溴碘苯，但并不仅限于这两种化合物，在本发明的其他实施例中，可以根据所需调整为其他化合物，但制备方法基本相同，在此不一一列举。
本发明实施例中所制得热活化延迟荧光材料的荧光发射光谱如图3所示。其基于B3LYP理论所计算出的光致发光峰(PL Peak)、最低单重态(S 1)、最低三重态能级(T 1)、最低单重态和三重能级差(ΔEST)以及光致发光量子效率(PLQY)如表1所示：
Figure PCTCN2019088078-appb-000008
表1
本发明实施例中所提供的一种热活化延迟荧光材料，其分子结构中的两个苯环通过饱和七元环进行连接，能够有效抑制分子间的π-π堆积，从而获得高的光致发光量子效率(PLQY)，并且其给电子能力介于二苯胺和吖啶之间，能够有效减低电子受体和电子给体之间的HOMO和LUMO的重叠程度，获得最低单重态和三重能级差较小的热活化延迟荧光材料，从而大大减少了发光淬灭现象，提高了显示器件的工作效率。
本发明实施例中所提供的一种热活化延迟荧光材料制备方法，其工艺简单，纯化容易，产率高。
本发明实施例中还提供一种显示装置，如图4所示，所述显示装置中包括一基板101、一第一电极层102、一注入层103、一空穴传输层104、一发光层105、一电子传输层106以及一第二电极层107。
所述基板101为玻璃基板，用于保护显示装置100的整体结构。所述第一电极层102设于基板101上，其为氧化铟锡透明导电玻璃，用于传输电流。所述注入层103设于所述第一电极层102上，其材料为2,3,6,7,10,11-六氰基-1,4,5,8,9,12-六氮杂苯并菲(HATCH)，用于将空穴能从所述第一电极层102有效地注入到器件中。所述空穴传输层104设于所述注入层103上，其材料为4,4'-环己基二[N,N-二(4-甲基苯基)苯胺](TAPC)，用于将从电极注入的空穴传输至所述发光层105。所述发光层105设于所述空穴传输层104上，其材料中包含所述热活化延迟荧光材料，其将电能转化为光能，从而为显示装置100提供光源。所述电子传输层106设于所述发光层105上，其材料为1,3,5-三(3-(3-吡啶基)苯基)苯(Tm3PyPB)，用于将从电极注入的电子传输至所述发光层105。所述第二电极层107设于所述电子传输层106上，其材料为氟化锂或铝。
当元件受到直流电所衍生的顺向偏压时，外加之电压能量将驱动电子与空穴分别由所述空穴传输层103和所述电子传输层105注入所述发光层104，并在所述发光层104中相遇、结合，即形成所谓的电子-空穴复合。而当化学分子受到外来能量激发后，若电子自旋和基态电子成对，则为单重态，其所释放的光为所谓的萤光。反之，若激发态电子和基态电子自旋不成对且平行，则称为三重态，其所释放的光为所谓的磷光。
为了更好的说明本发明中的热活化延迟荧光材料的性能，对包含所述热活化延迟荧光材料的最终产物显示装置100进行了性能测试。本次测试主要检测了最高亮度、电致发光峰(EL Peak)以及最大外量子效率，具体数据如表2所示。
最高亮度(cd/m2) EL peak(nm) 最大外量子效率(％)
3395 613 22
表2
其中，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。
由表2可知，本发明的近红外光热激活延迟荧光材料具有优良的发光性能，由其制作的发光层105荧光效率更高，稳定性更好，从而也提高了显示装置100的发光效率以及使用寿命。
本发明实施例中所提供的一种显示装置，所述显示装置的发光层中包含所述热活化延迟荧光材料，使发光层的荧光效率更高，稳定性更好，从而也提高了显示装置的发光效率以及使用寿命。
虽然在本文中参照了特定的实施方式来描述本发明，但是应该理解的是，这些实施例仅仅是本发明的原理和应用的示例。因此应该理解的是，可以对示例性的实施例进行许多修改，并且可以设计出其他的布置，只要不偏离所附权利要求所限定的本发明的精神和范围。应该理解的是，可以通过不同于原始权利要求所描述的方式来结合不同的从属权利要求和本文中所述的特征。还可以理解的是，结合单独实施例所描述的特征可以使用在其他所述实施例中。

Claims (10)

  1. 一种热活化延迟荧光材料，其中，所述热活化延迟荧光材料中包括电子给体与电子受体；其中，所述电子给体中包括至少两个苯环以及连接在两个苯环之间的七元环。
  2. 如权利要求1所述的热活化延迟荧光材料，其中，所述电子给体的分子结构中包括以下结构中的一种：
    Figure PCTCN2019088078-appb-100001
  3. 如权利要求1所述的热活化延迟荧光材料，其中，所述电子受体的分子结构中包括以下结构中的一种：
    Figure PCTCN2019088078-appb-100002
  4. 一种热活化延迟荧光材料的制备方法，其包括以下步骤：
    合成第一目标物：
    将电子给体、电子受体以及催化剂置于反应容器中，得到反应液，在氩气环境下充分反应得到混合溶液，所述混合溶液中具有反应生成的目标物；
    萃取第一目标物：
    将所述混合溶液冷却至室温，在反应液中加入二氯甲烷进行萃取，得到所述目标物；
    纯化处理第一目标物：
    使用淋洗液，通过硅胶柱层析方法纯化所述目标物，得到所述热活化延迟荧光材料。
  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，
    所述合成第一目标物步骤中：所述催化剂为甲苯、碳酸钾和四三苯基膦钯；
    所述电子给体、所述电子受体、所述甲苯和所述碳酸钾一起放置于所述反应容器中，再将所述反应容器放置于氩气环境中，并往所述反应容器中加入所述四三苯基磷钯，得到反应液。
  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，
    所述纯化处理目标物步骤中，所述硅胶柱层析方法中的淋洗液为石油醚和二氯甲烷，所述石油醚和所述二氯甲烷的体积比为1:1。
  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，
    在所述合成第一目标物步骤前还包括形成电子给体步骤，
    所述形成电子给体步骤包括以下步骤：
    合成第二目标物：
    将第一化合物、第二化合物以及催化剂置于反应容器中，得到反应液，在氩气环境下充分反应得到混合溶液，所述混合溶液中具有反应生成的目标物；
    萃取第二目标物：
    将所述混合溶液冷却至室温，萃取所述混合溶液中的所述目标物；
    纯化处理第二目标物：
    对所述目标物进行纯化处理，得到具有所述电子给体结构的第三化合物；
    其中，所述第一化合物的结构中具有至少两个苯环以及连接在两个苯环之间的七元环；所述第二化合物的结构中具有至少一个苯环。
  8. 如权利要求5所述的热活化延迟荧光材料的制备方法，其中，
    所述催化剂为三(二亚苄基丙酮)二钯、三叔丁基膦·四氟硼酸盐、叔丁醇钠和甲苯。
  9. 一种显示装置，其包括：
    一基板；
    一第一电极层，设于所述基板上；
    一注入层，设于所述第一电极层上；
    一空穴传输层，设于所述注入层上；
    一发光层，设于所述空穴传输层上；
    一电子传输层，设于所述发光层上；
    一第二电极层，设于所述电子传输层上；
    其中，所述发光层包含如权利要求1所述的热活化延迟荧光材料。
  10. 如权利要求9所述的显示装置，其中，
    所述注入层的材料为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为4,4'-环己基二[N,N-二(4-甲基苯基)苯胺]；
    所以电子传输层的材料为1,3,5-三(3-(3-吡啶基)苯基)苯。
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