WO2020191866A1 - 热活化延迟荧光材料及其制备方法、有机发光器件 - Google Patents

热活化延迟荧光材料及其制备方法、有机发光器件 Download PDF

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WO2020191866A1
WO2020191866A1 PCT/CN2019/086115 CN2019086115W WO2020191866A1 WO 2020191866 A1 WO2020191866 A1 WO 2020191866A1 CN 2019086115 W CN2019086115 W CN 2019086115W WO 2020191866 A1 WO2020191866 A1 WO 2020191866A1
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thermally activated
fluorescent material
delayed fluorescent
activated delayed
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张曲
吴凯龙
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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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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D219/00Heterocyclic compounds containing acridine or hydrogenated acridine ring systems
    • C07D219/14Heterocyclic compounds containing acridine or hydrogenated acridine ring systems with hydrocarbon radicals, substituted by nitrogen atoms, attached to the ring nitrogen atom
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D265/00Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
    • C07D265/281,4-Oxazines; Hydrogenated 1,4-oxazines
    • C07D265/341,4-Oxazines; Hydrogenated 1,4-oxazines condensed with carbocyclic rings
    • C07D265/38[b, e]-condensed with two six-membered rings
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    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • HELECTRICITY
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    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/10OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers

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  • the invention relates to the field of display technology, in particular to a thermally activated delayed fluorescent material, a preparation method thereof, and an organic light-emitting device.
  • OLED Organic Light-Emitting Diode
  • the photoelectric conversion efficiency is one of the important parameters for evaluating the performance of OLEDs.
  • various luminescent materials based on fluorescence and phosphorescence have been developed.
  • OLEDs based on fluorescent materials have the characteristics of high stability, but are limited by the laws of quantum statistics. Under the action of electrical activation, the ratio of singlet excited state excitons to triplet excited state excitons is 1:3, resulting in fluorescence The internal electroluminescence quantum efficiency of the material is limited to 25%; phosphorescent materials can use singlet excited state excitons and triplet excited state excitons due to the spin-orbit coupling effect of heavy atoms. Up to 100%, but phosphorescent-based OLED materials mostly use precious metals, which are not only costly, but also environmentally unfriendly.
  • the present invention provides a thermally activated delayed fluorescent material, which can solve the lack of existing thermally activated delayed fluorescent materials, and the efficiency decay in OLED devices is relatively fast, and the stability of the device is not high, thereby affecting the performance of the OLED device problem.
  • the present invention provides a thermally activated delayed fluorescent material, the chemical structural formula of the thermally activated delayed fluorescent material is shown in general formula (A):
  • the R group is a diphenylamine group.
  • the R group is selected from one of carbazole-based groups and phenoxazine-based groups.
  • the R group is selected from one of the following groups:
  • the present invention also provides a method for preparing a thermally activated delayed fluorescent material, the chemical structural formula of the thermally activated delayed fluorescent material is shown in general formula (A):
  • the R group is a diphenylamine group
  • the preparation method of the material includes the following steps:
  • the X group is a halogen atom other than the fluorine atom
  • the second reactant is selected from one of the following structural formulas:
  • the temperature of the heat treatment is 110 degrees Celsius, and the time of the heat treatment is 24 hours.
  • the basic compound is sodium tert-butoxide
  • the solvent is toluene from which water and oxygen are removed.
  • the S40 includes:
  • S402 Extract three times with dichloromethane, combine the organic phases, and spin into silica gel to obtain the organic mixture.
  • the S50 includes:
  • S502 Purify the light blue powder by using a sublimation apparatus to obtain the thermally activated delayed fluorescent material.
  • the X group is a bromine atom.
  • the R group is selected from one of carbazole-based groups and phenoxazine-based groups.
  • the R group is selected from one of the following groups:
  • the present invention also provides an organic electroluminescent device, which includes an anode, a light-emitting layer, and a cathode that are sequentially arranged on the substrate.
  • the light-emitting layer includes an organic material layer, wherein the organic material layer is thermally activated.
  • Preparation of delayed fluorescent material the chemical structural formula of the thermally activated delayed fluorescent material is shown in general formula (A):
  • the R group is a diphenylamine group.
  • the R group is selected from one of carbazole-based groups and phenoxazine-based groups.
  • the R group is selected from one of the following groups:
  • the substrate is a thin film transistor array substrate.
  • the light-emitting layer further includes a hole injection layer, a hole transport layer, an electron transport layer, and an electron injection layer sequentially disposed on the substrate.
  • the organic material layer is disposed between the hole transport layer and the electron transport layer.
  • the anode is made of indium tin oxide material.
  • the cathode includes a lithium fluoride film layer and an aluminum film layer.
  • the present invention uses tetrastyrene as the nucleus and connects carbazole, phenoxazine and other groups to construct a high-efficiency deep blue thermally activated delayed fluorescent material, so that the organic electric
  • the external quantum efficiency of the electroluminescent device is improved and the efficiency decays slowly, thereby increasing the service life of the organic electroluminescent device.
  • Figure 1 is a flow chart of the steps of the method for preparing thermally activated delayed fluorescent material of the present invention
  • FIG. 2 is a schematic diagram of the structure of the organic light emitting device of the present invention.
  • Figure 3 shows the electroluminescence spectra of compound 1, compound 2 and compound 3 at room temperature and atmospheric pressure.
  • the present invention is aimed at the existing thermally activated delayed fluorescent materials. Due to the lack of types, the material selectivity is not much, and the efficiency of the materials used in OLED devices is relatively fast, resulting in low stability of the OLED device, thereby affecting the OLED device. The performance problem of this embodiment can solve the defect.
  • the present invention provides a thermally activated delayed fluorescent material, the chemical structural formula of which is shown in general formula (A):
  • the R group is a diphenylamine group.
  • the R group is selected from one of carbazole-based groups, phenoxazine-based groups or other diphenylamine-based groups.
  • the R group can be selected from one of the following groups:
  • the present invention also provides a method for preparing the above thermally activated delayed fluorescent material, which includes the following steps:
  • the X group is a halogen atom other than the fluorine atom
  • the X group may be a bromine atom
  • the second reactant may be selected from one of the following structural formulas:
  • the temperature of the heat treatment is 110 degrees Celsius, and the time of the heat treatment is 24 hours.
  • the basic compound is sodium tert-butoxide, and the solvent is toluene from which water and oxygen are removed.
  • the S40 includes: first cooling the reaction solution to room temperature, then pour it into ice water; then extract three times with dichloromethane, combine the organic phases, and spin into silica gel to obtain the organic mixture.
  • the S50 includes: firstly, using a column chromatography method to separate the organic mixture to obtain a light blue powder; and then using a sublimation apparatus to purify the light blue powder to obtain the thermally activated delayed fluorescent material.
  • the palladium acetate is a catalyst
  • tri-tert-butylphosphine tetrafluoroborate is a catalyst ligand
  • the catalyst can also be other palladium catalysts.
  • the vacuum glove box is filled with an inert gas
  • the toluene is a solvent
  • the sodium tert-butoxide is an alkaline substance, which can remove acidic substances in subsequent reaction products.
  • the two-neck flask was heated at a constant temperature and reacted at 110 degrees Celsius for 24 hours to obtain a reaction solution.
  • reaction solution was cooled to room temperature, the reaction solution was poured into 50 ml of ice water, extracted three times with dichloromethane, and the organic phases were combined and spun into silica gel to obtain an organic mixed mixture.
  • volume ratio of methylene chloride to n-hexane in column chromatography is 1:5.
  • the chemical molecular formula of the thermally activated delayed fluorescent material is C 56 H 42 F 4 N 2 , the theoretical relative molecular mass is 818.96, and the relative molecular mass of the compound 1 measured by the mass spectrometer is 818.33, which is close to the theoretical value.
  • Compound 1 is an ideal target compound.
  • the structural formula of the thermally activated delayed fluorescent material synthesized in this implementation is as follows:
  • the two-neck bottle was placed in a vacuum glove box, and 12 millimoles (1.12 g) of sodium tert-butoxide (NaOt-Bu) and 40 ml of toluene removed from water and oxygen were added to the two-neck bottle to obtain The second mixture.
  • NaOt-Bu sodium tert-butoxide
  • the two-neck flask was heated at a constant temperature and reacted at 110 degrees Celsius for 24 hours to obtain a reaction solution.
  • reaction solution was cooled to room temperature, the reaction solution was poured into 50 ml of ice water, extracted three times with dichloromethane, and the organic phases were combined and spun into silica gel to obtain an organic mixed mixture.
  • volume ratio of methylene chloride to n-hexane in column chromatography is 1:4.
  • the chemical formula of the thermally activated delayed fluorescent material is C 50 H 30 F 4 N 2 O 2 , and the theoretical relative molecular mass is 766.80.
  • the relative molecular mass of the compound 2 measured by the mass spectrometer is 766.22, which is close to the theoretical value. It shows that the compound 2 is an ideal target compound.
  • the two-neck flask was heated at a constant temperature and reacted at 110 degrees Celsius for 24 hours to obtain a reaction solution.
  • reaction solution was cooled to room temperature, the reaction solution was poured into 50 ml of ice water, extracted three times with dichloromethane, and the organic phases were combined and spun into silica gel to obtain an organic mixed mixture.
  • volume ratio of methylene chloride to n-hexane in column chromatography is 1:6.
  • the chemical molecular formula of the thermally activated delayed fluorescent material is C 76 H 50 F 4 N 2 , and the theoretical relative molecular mass is 1067.24.
  • the relative molecular mass of the compound 3 measured by the mass spectrometer is 1066.39, which is close to the theoretical value.
  • Compound 3 is an ideal target compound.
  • PL Peak is the photoluminescence peak
  • S 1 is the lowest singlet energy level
  • T 1 is the lowest triplet energy level
  • Est is the electrochemical energy level
  • HOMO is the highest molecular orbital energy level
  • LUMO is the lowest molecular energy level. Account for orbital energy level.
  • the luminescence spectrum curves of the three compounds are in the same direction and basically coincide.
  • the photoluminescence peaks of the three compounds are around 430 nm, indicating that the synthesized compound is a deep blue material.
  • the S 1 state of the three compounds is higher in energy than the T I state, and the energy difference between the two is about 0.05 eV.
  • the energy difference between the two is small enough, and reverse intersystem crossing occurs within the molecules, resulting in Delayed fluorescence.
  • the present invention also provides an organic light-emitting device 100 which includes a substrate 10, an anode 20, a light-emitting layer 30, and a cathode 40 which are sequentially disposed on the substrate.
  • the luminescent layer includes the thermally activated delayed fluorescent material prepared by the above method
  • the substrate 100 may be a thin film transistor array substrate, and the light-emitting layer 30 includes a hole injection layer, a hole transport layer, an organic material layer, an electron transport layer, and an electron injection layer sequentially disposed on the substrate 100.
  • the light-emitting layer 30 includes a hole injection layer, a hole transport layer, an organic material layer, an electron transport layer, and an electron injection layer sequentially disposed on the substrate 100.
  • the anode 20 is made of indium tin oxide material, and the thickness of the anode 20 is 50 nanometers.
  • the hole injection layer and the hole transport layer are a mixture of poly3,4-ethylenedioxythiophene and polystyrene sulfonate, and the total thickness of the hole injection layer and the hole transport layer Is 50 nanometers.
  • the organic material layer is a thermally activated delayed fluorescent material prepared by the above method, and the thickness of the organic material layer is 40 nanometers.
  • the electron transport layer is 1,3,5-tris(3-(3-pyridyl)phenyl)benzene, and the thickness of the electron transport layer is 40 nanometers.
  • the cathode 40 is a composite cathode and includes a lithium fluoride film layer and an aluminum film layer, the thickness of the lithium fluoride film layer is 1 nanometer, and the thickness of the aluminum film layer is 100 nanometers.
  • a mixture of poly3,4-ethylenedioxythiophene and polystyrene sulfonate and the above thermally activated delayed fluorescent material are sequentially spin-coated on the anode 10
  • 1,3,5-tris(3-(3-pyridyl)phenyl)benzene, lithium fluoride, and aluminum materials are sequentially vapor-deposited under high vacuum conditions to prepare the organic light-emitting device.
  • organic light-emitting device 1 organic light-emitting device 2, and organic light-emitting device 3 prepared separately from compound 1, compound 2, and compound 3 as examples, the current-brightness-voltage characteristics of the device are measured under room temperature and atmospheric pressure, such as Table 2 shows.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Electroluminescent Light Sources (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)

Abstract

一种所述热活化延迟荧光材料的化学结构式为 (A), R基团为二苯胺类基团。通过以四苯乙烯为核,连接咔唑、吩噁嗪等基团,从而构建出高效率的深蓝光热活化延迟荧光材料,使得基于该材料制备的有机电致发光器件的外量子效率得到提高且效率衰减缓慢,进而提高有机电致发光器件的使用寿命。

Description

热活化延迟荧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,尤其涉及一种热活化延迟荧光材料及其制备方法、有机发光器件。
背景技术
OLED(Organic Light-Emitting Diode,有机发光二极管)在照明、显示等领域具有很大的应用价值且得到广泛应用。光电转换效率是评价OLED性能的重要参数之一,为提高OLED的发光效率,各种基于荧光、磷光的发光材料被开发出来。
基于荧光材料的OLED具有稳定性高的特点,但受限于量子统计学定律,在电激活作用下,产生的单重激发态激子和三重激发态激子的比例为1:3,导致荧光材料的内部电致发光量子效率被限制在25%;磷光材料由于具有重原子的旋轨耦合作用,可同时利用单重激发态激子和三重激发态激子,其理论内电子发光量子效率能够达到100%,但基于磷光的OLED材料多采用贵重金属,不仅成本高,而且对环境不友好。
为了克服这上述两种材料的缺点,专家提出利用三重激发态激子通过热活化回到单重态,再辐射跃迁回到基态发光,使得理论内量子效率达到100%。这样便可利用不含重金属原子的有机化合物实现与磷光OLED相匹配的高效率。近年来,虽然TADF(Thermally Activated Delayed Fluorescence,热活化延迟荧光)材料被报道过,但高效稳定的红、绿、蓝TADF材料的种类较少, 材料的可选择性仍然不足,多数材料在OLED器件中效率衰减较快,且器件的稳定性也有待提高。
发明内容
本发明提供一种热活化延迟荧光材料,能够解决现有的热活化延迟荧光材料的种类缺乏,且OLED器件中的效率衰减性较快,且器件的稳定性不高,进而影响OLED器件的性能问题。
为解决上述问题,本发明提供的技术方案如下:
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的化学结构式如通式(A)所示:
Figure PCTCN2019086115-appb-000001
其中,R基团为二苯胺类基团。
在本发明的一种实施例中,所述R基团选自咔唑类基团、吩噁嗪类基团中的一种。
在本发明的一种实施例中,所述R基团选自以下基团中的一种:
Figure PCTCN2019086115-appb-000002
本发明还提供一种热活化延迟荧光材料的制备方法,所述热活化延迟荧光材料的化学结构式如通式(A)所示:
Figure PCTCN2019086115-appb-000003
其中,R基团为二苯胺类基团,所述材料的制备方法包括以下步骤:
S10,将第一反应物、第二反应物以及催化剂混合在容器中,得到第一混合物,所述第二反应物为二苯胺类化合物,所述第一反应物的化学结构式如通式(D)所示:
Figure PCTCN2019086115-appb-000004
X基团为除去氟原子以外的卤素原子;
S20,将所述容器置于真空手套箱中,向所述手套箱内的容器中加入碱性化合物和溶剂,得到第二混合物;
S30,对装有所述第二混合物的容器进行热处理,得到反应液;
S40,对所述反应液进行冷却、萃取,得到有机混合物;
S50,对所述有机混合物进行除杂处理,得到所述热活化延迟荧光材料。
在本发明的一种实施例中,所述第二反应物选自以下结构式中的一种:
Figure PCTCN2019086115-appb-000005
在本发明的一种实施例中,所述S30中,所述热处理的温度为110摄氏度,所述热处理的时间为24小时。
在本发明的一种实施例中,所述碱性化合物为叔丁醇钠,所述溶剂为除去水氧的甲苯。
在本发明的一种实施例中,所述S40包括:
S401,将反应液冷却至室温后,倒入冰水中;
S402,利用二氯甲烷萃取三次,合并有机相,旋成硅胶,得到所述有机混合物。
在本发明的一种实施例中,所述S50包括:
S501,利用柱层析方法,将所述有机混合物进行分离,得到淡蓝色粉末;
S502,利用升华仪对所述淡蓝色粉末进行纯化,得到所述热活化延迟荧光材料。
在本发明的一种实施例中,所述X基团为溴原子。
在本发明的一种实施例中,所述R基团选自咔唑类基团、吩噁嗪类基团中的一种。
在本发明的一种实施例中,所述R基团选自以下基团中的一种:
Figure PCTCN2019086115-appb-000006
本发明还提供一种有机电致发光器件,包括衬底依次设置于所述衬底上的阳极、发光层以及阴极,所述发光层包括有机材料层,其中,所述有机材料层采用热活化延迟荧光材料制备,所述热活化延迟荧光材料的化学结构式如通式(A)所示:
Figure PCTCN2019086115-appb-000007
其中,R基团为二苯胺类基团。
在本发明的一种实施例中,所述R基团选自咔唑类基团、吩 噁嗪类基团中的一种。
在本发明的一种实施例中,所述R基团选自以下基团中的一种:
Figure PCTCN2019086115-appb-000008
在本发明的一种实施例中,所述衬底为薄膜晶体管阵列基板。
在本发明的一种实施例中,所述发光层还包括依次设置于所述衬底上的空穴注入层、空穴传输层、电子传输层、以及电子注入层。
在本发明的一种实施例中,所述有机材料层设置于所述空穴传输层与所述电子传输层之间。
在本发明的一种实施例中,所述阳极为氧化铟锡材料。
在本发明的一种实施例中,所述阴极包括氟化锂膜层和铝膜层。
本发明的有益效果为:本发明通过利用四苯乙烯为核,连接 咔唑、吩噁嗪等基团,从而构建出高效率的深蓝光热活化延迟荧光材料,使得基于该材料制备的有机电致发光器件的外量子效率得到提高且效率衰减缓慢,进而提高有机电致发光器件的使用寿命。
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为本发明的热活化延迟荧光材料的制备方法的步骤流程图;
图2为本发明的有机发光器件的结构示意图;
图3为室温大气压下,化合物1、化合物2以及化合物3的电致发光光谱图。
具体实施方式
以下各实施例的说明是参考附加的图示,用以例示本发明可用以实施的特定实施例。本发明所提到的方向用语,例如[上]、[下]、[前]、[后]、[左]、[右]、[内]、[外]、[侧面]等,仅是参考附加图式的方向。因此,使用的方向用语是用以说明及理解本发明,而非用以限制本发明。在图中,结构相似的单元是用以相同 标号表示。
本发明针对现有的热活化延迟荧光材料,由于种类缺乏,材料的选择性不多,且应用于OLED器件中的材料效率衰减性较快,导致OLED器件的稳定性不高,进而影响OLED器件的性能问题,本实施例能够解决该缺陷。
本发明提供一种热活化延迟荧光材料,其化学结构式如通式(A)所示:
Figure PCTCN2019086115-appb-000009
其中,R基团为二苯胺类基团。
具体地,所述R基团选自咔唑类基团、吩噁嗪类基团或其他二苯胺类基团中的一种。
所述R基团可选自以下基团中的一种:
Figure PCTCN2019086115-appb-000010
通过以四苯乙烯为核,连接咔唑、吩噁嗪等基团,从而达到构建高效率的深蓝光D-A-D型TADF材料,且以此材料制备的有机电致发光器件的外量子效率高,效率衰减缓慢。
如图1所示,本发明还提供上述热活化延迟荧光材料的制备方法,包括以下步骤:
S10,将第一反应物、第二反应物以及催化剂混合在容器中,得到第一混合物,所述第二反应物为二苯胺类化合物,所述第一反应物的化学结构式如通式(D)所示:
Figure PCTCN2019086115-appb-000011
X基团为除去氟原子以外的卤素原子;
S20,将所述容器置于真空手套箱中,向所述手套箱内的容 器中加入碱性化合物和溶剂,得到第二混合物;
S30,对装有所述第二混合物的容器进行热处理,得到反应液;
S40,对所述反应液进行冷却、萃取,得到有机混合物;
S50,对所述有机混合物进行除杂处理,得到所述热活化延迟荧光材料。
具体地,所述X基团可为溴原子,所述第二反应物可选自以下结构式中的一种:
Figure PCTCN2019086115-appb-000012
所述S30中,所述热处理的温度为110摄氏度,所述热处理的时间为24小时。
所述碱性化合物为叔丁醇钠,所述溶剂为除去水氧的甲苯。
所述S40包括:先将反应液冷却至室温后,倒入冰水中;再利用二氯甲烷萃取三次,合并有机相,旋成硅胶,得到所述有机混合物。
所述S50包括:首先利用柱层析方法,将所述有机混合物进行分离,得到淡蓝色粉末;再利用升华仪对所述淡蓝色粉末进行纯化,得到所述热活化延迟荧光材料。
下面结合具体实施例对所述制备方法进行详细说明。
实施例一
本实施例合成的热活化延迟荧光材料的结构式如下:
Figure PCTCN2019086115-appb-000013
首先,向100毫升的二口瓶中,加入5毫摩尔(2.80克)的(E)-1,2-二(4-溴苯基)-1,2-二(3,5-二氟苯基)乙烯、10毫摩尔(2.09克)的9,10二氢-9,9-二苯基吖啶、0.4毫摩尔(90毫克)的醋酸钯(Pd(OAc) 2)、以及1.2毫摩尔(0.34克)的三叔丁基膦四氟硼酸盐((t-Bu) 3HPBF 4),得到第一混合物。
其中,所述醋酸钯为催化剂,三叔丁基膦四氟硼酸盐为催化剂配体,所述催化剂还可为其他钯催化剂。
然后,将所述二口瓶置于真空手套箱中,再向所述二口瓶瓶中加入12毫摩尔(1.12克)的叔丁醇钠(NaOt-Bu)和40毫升除去水氧的甲苯,得到第二混合物。
其中,所述真空手套箱中充有惰性气体,所述甲苯为溶剂,所述叔丁醇钠为碱性物质,可除去后续反应产物中的酸性物质。
之后,对所述二口瓶进行恒温加热,在110摄氏度下反应24小时,得到反应液。
再将所述反应液冷却至室温,将所述反应液倒入50毫升的冰水中,利用二氯甲烷萃取三次,合并有机相,并旋成硅胶,得到有机混合混合物。
然后,利用柱层析法,对所述有机混合物进行分离纯化,得到2.7克的淡蓝色粉末,产率为67%。
其中,柱层析中的二氯甲烷与正己烷的体积比为1:5。
最后,利用升华仪对所述淡蓝色粉末进行纯化,得到2.1克的化合物1。
本实施例中的所述热活化延迟荧光材料的合成路线为:
Figure PCTCN2019086115-appb-000014
所述热活化延迟荧光材料的化学分子式为C 56H 42F 4N 2,理论相对分子质量为818.96,质谱仪测得的所述化合物1的相对分子质量为818.33,与理论值接近,说明该化合物1为理想的目标化合物。
实施例二
本实施合成的热活化延迟荧光材料的结构式如下:
Figure PCTCN2019086115-appb-000015
首先,向100毫升的二口瓶中加入5毫摩尔(2.80克)的(E)-1,2-二(4-溴苯基)-1,2-二(3,5-二氟苯基)乙烯、12毫摩尔(2.2克)的吩噁嗪、0.4毫摩尔(90毫克)的醋酸钯(Pd(OAc) 2)、以及1.2毫摩尔(0.34克)的三叔丁基膦四氟硼酸盐((t-Bu) 3HPBF 4),得到第一混合物。
然后,将所述二口瓶置于真空手套箱中,向所述二口瓶中加入12毫摩尔(1.12克)的叔丁醇钠(NaOt-Bu)和40毫升除去水氧的甲苯,得到第二混合物。
之后,对所述二口瓶进行恒温加热,在110摄氏度下反应24小时,得到反应液。
再将所述反应液冷却至室温,将所述反应液倒入50毫升的冰水中,利用二氯甲烷萃取三次,合并有机相,并旋成硅胶,得到有机混合混合物。
然后,利用柱层析法,对所述有机混合物进行分离纯化,得到2.4克的淡蓝色粉末,产率为63%。
其中,柱层析中的二氯甲烷与正己烷的体积比为1:4。
最后,利用升华仪对所述淡蓝色粉末进行纯化,得到1.9克的化合物2。
本实施例中的所述热活化延迟荧光材料的合成路线为:
Figure PCTCN2019086115-appb-000016
所述热活化延迟荧光材料的化学分子式为C 50H 30F 4N 2O 2,理论相对分子质量为766.80,质谱仪测得的所述化合物2的相对分子质量为766.22,与理论值接近,说明该化合物2为理想目标化合物。
实施例三
本实施例合成的热活化延迟荧光材料的结构式如下:
Figure PCTCN2019086115-appb-000017
首先,向100毫升的二口瓶中,加入5毫摩尔(2.80克)的(E)-1,2-二(4-溴苯基)-1,2-二(3,5-二氟苯基)乙烯、11毫摩尔(3.67克)9,9-二苯基-9,10-二氢吖啶、0.4毫摩尔(90毫克)的醋酸钯(Pd(OAc) 2)、以及1.2毫摩尔(0.34克)的三叔丁基膦四氟硼酸盐((t-Bu) 3HPBF 4),得到第一混合物。
然后,将所述二口瓶置于真空手套箱中,再向所述二口瓶瓶中加入12毫摩尔(1.12克)的叔丁醇钠(NaOt-Bu)和40毫升除去水氧的甲苯,得到第二混合物。
之后,对所述二口瓶进行恒温加热,在110摄氏度下反应24小时,得到反应液。
再将所述反应液冷却至室温,将所述反应液倒入50毫升的冰水中,利用二氯甲烷萃取三次,合并有机相,并旋成硅胶,得到有机混合混合物。
然后,利用柱层析法,对所述有机混合物进行分离纯化,得到3.0克的淡蓝色粉末,产率为56%。
其中,柱层析中的二氯甲烷与正己烷的体积比为1:6。
最后,利用升华仪对所述淡蓝色粉末进行纯化,得到2.6克的化合物3。
本实施例中的所述热活化延迟荧光材料的合成路线为:
Figure PCTCN2019086115-appb-000018
所述热活化延迟荧光材料的化学分子式为C 76H 50F 4N 2,理论相对分子质量为1067.24,质谱仪测得的所述化合物3的相对分子质量为1066.39,与理论值接近,说明该化合物3为理想的目标化合物。
上述3个实施例中合成的化合物1、化合物2、以及化合物3的分子能级如下表1所示。
表1
Figure PCTCN2019086115-appb-000019
Figure PCTCN2019086115-appb-000020
其中,PL Peak为光致发光峰值,S 1最低单重态能级,T 1是最低三重态能级,Est为电化学能级,HOMO为分子最高已占轨道能级,LUMO为分子最低未占轨道能级。
如图3所示,三种化合物的发光光谱曲线走向一致,基本重合,三种化合物的光致发光峰值在430纳米附近,说明合成的化合物为深蓝光材料。
从表1中可看出,三种化合物的HOMO与LUMO的能隙较宽,两者之间的能隙在3.0eV左右。
三种化合物的S 1态在能量上高于T I态,两者之间的能量差均约为0.05eV,两者之间的能量差足够小,分子内部发生反向系间窜越,产生延迟荧光。
如图2所示,本发明还提供一种有机发光器件100,所述有机发光器件100包括衬底10、依次设置于所述衬底上的阳极20、发光层30、以及阴极40。所述发光层包括上述方法制备的热活化延迟荧光材料
其中,所述衬底100可为薄膜晶体管阵列基板,所述发光层30包括依次设置在所述衬底100上的空穴注入层、空穴传输层、有机材料层、电子传输层、电子注入层。
所述阳极20采用氧化铟锡材料,所述阳极20的厚度为50纳米。
所述空穴注入层和所述空穴传输层为聚3,4-乙撑二氧噻吩和聚苯乙烯磺酸盐的混合物,所述空穴注入层和所述空穴传输层 的总厚度为50纳米。
所述有机材料层为上述方法制备的热活化延迟荧光材料,所述有机材料层的厚度为40纳米。
所述电子传输层为1,3,5-三(3-(3-吡啶基)苯基)苯,所述电子传输层的厚度为40纳米。
所述阴极40为复合阴极,包括氟化锂膜层和铝膜层,所述氟化锂膜层的厚度为1纳米,所述铝膜层的厚度为100纳米。
在所述衬底100上形成所述阳极10之后,依次在所述阳极10上依次旋涂聚3,4-乙撑二氧噻吩和聚苯乙烯磺酸盐的混合物、上述热活化延迟荧光材料,之后在高真空条件下依次蒸镀1,3,5-三(3-(3-吡啶基)苯基)苯、氟化锂以及铝材料,从而制备成所述有机发光器件。
以化合物1、化合物2、化合物3分别制备而成的有机发光器件1、有机发光器件2、有机发光器件3为例,在室温大气压条件下,对器件进行电流-亮度-电压的特性测量,如表2所示。
表2
器件 最高亮度(cd/m 2) 启动电压(V) 色度坐标 最大外量子效率(%)
有机发光器件1 2103 4.4 (0.14,0.13) 12.3
有机发光器件2 2258 4.4 (0.14,0.13) 13.5
有机发光器件3 2079 4.5 (0.14,0.12) 12.1
有益效果:通过以四苯乙烯为核,连接咔唑、吩噁嗪等基团,构建出高效率的深蓝光热活化延迟荧光材料,使得基于该材料制备的有机电致发光器件的外量子效率得到提高且效率衰减缓慢,进而提高有机电致发光器件的使用寿命。
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 (20)

  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的化学结构式如通式(A)所示:
    Figure PCTCN2019086115-appb-100001
    其中,R基团为二苯胺类基团。
  2. 根据权利要求1所述的热活化延迟荧光材料,其中,所述R基团选自咔唑类基团、吩噁嗪类基团中的一种。
  3. 根据权利要求2所述的热活化延迟荧光材料,其中,所述R基团选自以下基团中的一种:
    Figure PCTCN2019086115-appb-100002
  4. 一种热活化延迟荧光材料的制备方法,其中,所述热活化 延迟荧光材料的化学结构式如通式(A)所示:
    Figure PCTCN2019086115-appb-100003
    其中,R基团为二苯胺类基团,所述材料的制备方法包括以下步骤:
    S10,将第一反应物、第二反应物以及催化剂混合在容器中,得到第一混合物,所述第二反应物为二苯胺类化合物,所述第一反应物的化学结构式如通式(D)所示:
    Figure PCTCN2019086115-appb-100004
    X基团为除去氟原子以外的卤素原子;
    S20,将所述容器置于真空手套箱中,向所述手套箱内的容器中加入碱性化合物和溶剂,得到第二混合物;
    S30,对装有所述第二混合物的容器进行热处理,得到反应液;
    S40,对所述反应液进行冷却、萃取,得到有机混合物;
    S50,对所述有机混合物进行除杂处理,得到所述热活化延迟荧光材料。
  5. 根据权利要求4所述的制备方法,其中,所述第二反应物选自以下结构式中的一种:
    Figure PCTCN2019086115-appb-100005
  6. 根据权利要求5所述的制备方法,其中,所述S30中,所述热处理的温度为110摄氏度,所述热处理的时间为24小时。
  7. 根据权利要求5所述的制备方法,其中,所述碱性化合物为叔丁醇钠,所述溶剂为除去水氧的甲苯。
  8. 根据权利要求7所述的制备方法,其中,所述S40包括:
    S401,将反应液冷却至室温后,倒入冰水中;
    S402,利用二氯甲烷萃取三次,合并有机相,旋成硅胶,得到所述有机混合物。
  9. 根据权利要求8所述的制备方法,其中,所述S50包括:
    S501,利用柱层析方法,将所述有机混合物进行分离,得到淡蓝色粉末;
    S502,利用升华仪对所述淡蓝色粉末进行纯化,得到所述热活化延迟荧光材料。
  10. 根据权利要求4所述的制备方法,其中,所述X基团为 溴原子。
  11. 根据权利要求4所述的制备方法,其中,所述R基团选自咔唑类基团、吩噁嗪类基团中的一种。
  12. 根据权利要求11所述的制备方法,其中,所述R基团选自以下基团中的一种:
    Figure PCTCN2019086115-appb-100006
  13. 一种有机电致发光器件,包括衬底、依次设置于所述衬底上的阳极、发光层以及阴极,所述发光层包括有机材料层,其中,
    所述有机材料层采用热活化延迟荧光材料制备,所述热活化延迟荧光材料的化学结构式如通式(A)所示:
    Figure PCTCN2019086115-appb-100007
    其中,R基团为二苯胺类基团。
  14. 根据权利要求13所述的有机电致发光器件,其中,所述R基团选自咔唑类基团、吩噁嗪类基团中的一种。
  15. 根据权利要求14所述的热活化延迟荧光材料,其中,所述R基团选自以下基团中的一种:
    Figure PCTCN2019086115-appb-100008
  16. 根据权利要求13所述的有机电致发光器件,其中,所述衬底为薄膜晶体管阵列基板。
  17. 根据权利要求13所述的有机电致发光器件,其中,所述发光层还包括依次设置于所述衬底上的空穴注入层、空穴传输层、电子传输层、以及电子注入层。
  18. 根据权利要求17所述的有机电致发光器件,其中,所述有机材料层设置于所述空穴传输层与所述电子传输层之间。
  19. 根据权利要求13所述的有机电致发光器件,其中,所述阳极为氧化铟锡材料。
  20. 根据权利要求13所述的有机电致发光器件,其中,所述阴极包括氟化锂膜层和铝膜层。
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YUNPENG QI , YONGTAO WANG , YONGJIANG YU , ZHIYONG LIU , YAN ZHANG , YU QI, CHANGTONG ZHOU: "Exploring highly efficient light conversion agents for agricultural film based on aggregation induced emission effects", JOURNAL OF MATERIALS CHEMISTRY C, vol. 4, 8 November 2016 (2016-11-08), pages 11291 - 11297, XP055738026, ISSN: 2050-7526, DOI: 10.1039/C6TC04215E *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113397502A (zh) * 2021-05-28 2021-09-17 北京理工大学 一种基于神经反馈的多模态数据采集设备
CN113397502B (zh) * 2021-05-28 2022-11-08 北京理工大学 一种基于神经反馈的多模态数据采集设备

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