WO2020124764A1 - 红光热活化延迟荧光材料、其制备方法及有机发光二极管器件 - Google Patents

红光热活化延迟荧光材料、其制备方法及有机发光二极管器件 Download PDF

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WO2020124764A1
WO2020124764A1 PCT/CN2019/075305 CN2019075305W WO2020124764A1 WO 2020124764 A1 WO2020124764 A1 WO 2020124764A1 CN 2019075305 W CN2019075305 W CN 2019075305W WO 2020124764 A1 WO2020124764 A1 WO 2020124764A1
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red
thermally activated
activated delayed
delayed fluorescent
fluorescent material
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罗佳佳
杨林
白亚梅
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Wuhan China Star Optoelectronics Semiconductor Display Technology Co Ltd
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Wuhan China Star Optoelectronics Semiconductor Display Technology Co Ltd
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Definitions

  • the invention relates to a red-light thermally activated delayed fluorescent material, its preparation method and organic light emitting diode (OLED) device, in particular to a red-light thermally activated delayed fluorescent material with high efficiency, its preparation method and organic Light emitting diode device.
  • OLED organic light emitting diode
  • Organic light-emitting diodes (organic light-emitting diodes, OLEDs) have active light emission that does not require a backlight, high luminous efficiency, large viewing angle, fast response speed, large temperature adaptation range, relatively simple production and processing technology, low driving voltage, The advantages of low energy consumption, light and thin structure, and flexible display have huge application prospects, which have attracted the attention of many researchers.
  • the luminescent guest material that plays a leading role is the most important.
  • the luminescent guest materials used in early OLEDs were fluorescent materials. Since the ratio of singlet and triplet excitons in OLED is 1:3, the theoretical internal quantum efficiency (IQE) of OLED based on fluorescent materials can only reach 25% , which greatly limits the application of fluorescent electroluminescent devices.
  • Another luminescent guest material is a heavy metal complex phosphorescent material. Due to the spin orbit coupling of heavy atoms, it can simultaneously use singlet and triplet excitons to achieve 100% IQE.
  • the commonly used heavy metals are precious metals such as Ir and Pt, and the phosphorescent luminescent materials of the heavy metal complexes have yet to be broken through in terms of red materials.
  • luminescent guest materials such as pure organic thermally activated delayed fluorescence (TADF) materials
  • TADF pure organic thermally activated delayed fluorescence
  • ⁇ EST minimum single triple energy level difference
  • TADF materials For TADF materials, fast reverse intersystem crossing constant (k RISC ) and high photoluminescence quantum yield (PLQY) are necessary conditions for the preparation of high-efficiency OLEDs. At present, TADF materials with the above conditions still belong to a few relative to the heavy metal Ir complex materials. In the red light field where phosphorescent heavy metal materials need to be broken through, TADF materials are few and far between.
  • k RISC fast reverse intersystem crossing constant
  • PLQY photoluminescence quantum yield
  • TADF materials with fast reverse intersystem crossing constant (k RISC ) and high photoluminescence quantum yield (PLQY) are still a minority relative to the heavy metal Ir complex materials.
  • the main object of the present invention is to provide a red-light thermally activated delayed fluorescent material and a preparation method thereof.
  • the molecular structure of the combined body (A) part can increase the electron donating ability of the electron donor part through different substituents, so that the red light thermally activated delayed fluorescent material has a low single triplet energy level To achieve red light emission.
  • Another object of the present invention is to provide an organic light emitting diode device comprising a light emitting material layer formed by the red thermally activated delayed fluorescent material.
  • an embodiment of the present invention provides a red-light thermally activated delayed fluorescent material, wherein the red-light thermally activated delayed fluorescent material has the following structure:
  • X 1 and X 2 are independently selected from isobutyl, methoxy or dimethylamino.
  • the red thermally activated delayed fluorescent material is
  • Another embodiment of the present invention provides a method for preparing a red-light thermally activated delayed fluorescent material, including the steps of: (1) placing a first reactant and a second reactant in a reaction vessel, wherein the first One reactant has a molecular structure of the following formula (A), and the second reactant has a molecular structure of the following formula (B):
  • the reaction is heated to above 120°C in an inert gas to produce a red-light thermally activated delayed fluorescent material.
  • the red-light thermally activated delayed fluorescent material has the following structural formula (I):
  • Y is F, Cl or Br;
  • X 1 and X 2 are independently selected from isobutyl, methoxy or dimethylamino.
  • the inert gas is argon.
  • the first reactant is And the second reactant is
  • the red thermally activated delayed fluorescent material is
  • Yet another embodiment of the present invention provides an organic light emitting diode device including: a transparent substrate; a transparent conductive layer provided on the transparent substrate; and a hole transport layer provided on the transparent A conductive layer; a luminescent material layer, disposed on the hole transport layer; an electron transport layer, disposed on the luminescent material layer; and a cathode layer, disposed on the electron transport layer, wherein the The light-emitting material layer contains the red-light thermally activated delayed fluorescent material described above.
  • the material of the transparent conductive layer is indium tin oxide.
  • the material of the hole transport layer is poly 3,4-ethylenedioxythiophene: polystyrene sulfonate (PEDOT: PSS).
  • the material of the electron transport layer is 1,3,5-tris(3-(3-pyridyl)phenyl)benzene, 1,3,5-tris(1-phenyl -1H-benzimidazol-2-yl)benzene or 3,3'-[5'-[3-(3-pyridyl)phenyl][1,1':3',1"-terphenyl]- 3,3"-diyl]dipyridine.
  • the thickness of the luminescent material layer is 15-20 nm.
  • the hole transport layer has a thickness of 40-50 nm.
  • the thickness of the electron transport layer is 30 to 40 nm.
  • the organic light emitting diode device has a maximum brightness of 1300 to 1800cd/m 2 .
  • the organic light emitting diode device has a maximum current efficiency of 25 to 35cd/A.
  • An embodiment of the present invention provides a red-light thermally activated delayed fluorescent material and a preparation method thereof.
  • the red-light thermally activated delayed fluorescent material has excellent light-emitting performance, and includes an electron donor (D) part and an electron acceptor
  • the molecular structure of the combined body (A) part can increase the electron donating ability of the electron donor part through different substituents, so that the red light thermally activated delayed fluorescent material has a low single triplet energy level .
  • Another embodiment of the present invention provides an organic light emitting diode device including a light emitting material layer formed by the red thermally activated delayed fluorescent material to achieve red light emission.
  • FIG. 1 is a schematic diagram of an organic light emitting diode device according to an embodiment of the invention.
  • the invention provides a red light thermally activated delayed fluorescent material, wherein the red light thermally activated delayed fluorescent material has the following structure:
  • X 1 and X 2 are independently selected from isobutyl, methoxy or dimethylamino.
  • the preparation method of the red-light thermally activated delayed fluorescent material includes the steps of: (S1) placing a first reactant and a second reactant in a reaction vessel, wherein the first reactant has a molecular structure as follows ( A), the second reactant has a molecular structure of the following formula (B):
  • Red light thermally activated delayed fluorescent material the red light thermally activated delayed fluorescent material has the following structural formula (I):
  • Y is F, Cl or Br
  • X 1 and X 2 are independently selected from isobutyl, methoxy or dimethylamino.
  • the inert gas is argon.
  • FIG. 1 shows a schematic diagram of an organic light emitting diode device according to an embodiment of the invention.
  • the organic light emitting diode device mainly includes a transparent conductive substrate 1, a hole transport layer 2, a light emitting material layer 3, an electron transport layer 4, and a cathode layer 5 formed by a transparent substrate and a transparent conductive layer.
  • the transparent conductive layer is disposed on the transparent substrate.
  • the transparent conductive layer may be, for example, an indium tin oxide (ITO) electrode, but it is not limited thereto, and generally known transparent electrode materials may be used.
  • ITO indium tin oxide
  • the material of the hole transport layer 2 may be, for example, poly 3,4-ethylenedioxythiophene: polystyrene sulfonate (PEDOT: PSS), but it is not limited thereto.
  • the thickness of the hole transport layer 2 is less than 50 nanometers, preferably 40 to 50 nanometers, and may be, for example, 50, 45 or 40 nanometers, but it is not limited thereto.
  • the luminescent material layer 3 includes a red-light thermally activated delayed fluorescent material, and its molecular structure is as follows:
  • X 1 and X 2 are independently selected from isobutyl (-C(CH 3 ) 3 ), methoxy (-OCH 3 ) or dimethylamino (-N(CH 3 ) 2 ).
  • the specific structure of the red-light thermally activated delayed fluorescent material is as follows: (1) to (3):
  • reaction solution was poured into 200 mL of ice water, extracted three times with dichloromethane, the organic phases were combined, spinned into silica gel, and column chromatography (dichloromethane: n-hexane, v: v, 1: 2) was separated and purified. Red powder 2.1g, yield 89%.
  • reaction solution was poured into 200 mL of ice water, extracted three times with dichloromethane, the organic phases were combined, spinned into silica gel, and column chromatography (dichloromethane: n-hexane, v: v, 1: 2) was separated and purified. Red powder 1.9g, yield 90%.
  • reaction solution was poured into 200 mL of ice water, extracted three times with dichloromethane, the organic phases were combined, spinned into silica gel, and column chromatography (dichloromethane: n-hexane, v: v, 1: 2) was separated and purified. Red powder 1.7g, yield 76%.
  • FIG. 2 shows the photoluminescence spectra of the red thermally activated delayed fluorescent materials of the above formulas (1) to (3) in toluene solution at room temperature.
  • FIG. 3 shows the transient photoluminescence spectra of the red thermally activated delayed fluorescent materials of the above formulas (1) to (3) in toluene solution at room temperature.
  • the thickness of the luminescent material layer 3 is less than 20 nanometers, preferably 15 to 20 nanometers, and may be, for example, 15, 17 or 20 nanometers, but it is not limited thereto.
  • the material of the electron transport layer 4 is 1,3,5-tris(3-(3-pyridyl)phenyl)benzene (Tm 3 PyPB), 1,3,5-tris(1-phenyl -1H-benzimidazol-2-yl)benzene (TPBI) or 3,3'-[5'-[3-(3-pyridyl)phenyl][1,1':3',1"-Triple Benzene]-3,3"-diyl]dipyridine (TmPyPB).
  • the thickness of the electron transport layer 4 is less than 40 nanometers, preferably 30 to 40 nanometers, and may be, for example, 30, 35 or 40 nanometers, but it is not limited thereto.
  • the organic light emitting diode device has a maximum brightness of 1300 to 1800 cd/m 2 (candle light/m 2 ), preferably 1465 to 1587 cd/m 2 .
  • the organic light emitting diode device has a maximum current efficiency of 25 to 35cd/A (candle light/ampere), preferably 27.3 to 29.1cd/A.
  • an organic light-emitting diode device is manufactured by a specific method: lining the washed conductive glass (ITO) Spin coating on the bottom, PESOT:PSS, and then vapor deposition of the red-light thermally activated delayed fluorescent material of the present invention, Tm 3 PyPB, 1 nm LiF and 100 nm Al under high vacuum conditions.
  • ITO washed conductive glass
  • PESOT:PSS washed conductive glass
  • the performance data of the above devices A1 to A3 are measured.
  • the current-brightness-voltage characteristics of the device are completed by a Keithley source measurement system (Keithley 2400 Sourcemeter, Keithley 2000 Currentmeter) with a corrected silicon photodiode, and the electroluminescence spectrum is measured by SPEX CCD3000 spectrometer of French JY company. All measurements are done in room temperature atmosphere. The measurement results are shown in Table 3 below.
  • device A3 has the highest brightness of 1587cd/m 2 and the highest current The efficiency is 29.1cd/A, and the maximum external quantum efficiency is 21.6%.

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Abstract

一种红光热活化延迟荧光材料、其制备方法及有机发光二极管器件。所述有机发光二极管器件包含一发光材料层(3)，所述发光材料层(3)包含所述红光热活化延迟荧光材料。所述红光热活化延迟荧光材料具有特定分子结构。所述有机发光二极管器件具有一最高亮度为1300至1800cd/m2，以及一最高电流效率为25至35cd/A。

Description

红光热活化延迟荧光材料、其制备方法及有机发光二极管器件 技术领域
本发明是有关于一种红光热活化延迟荧光材料、其制备方法及有机发光二极管(OLED)器件，特别是有关于一种具有高效率的红光热活化延迟荧光材料、其制备方法及有机发光二极管器件。
背景技术
有机电致发光二极管(organic light-emitting diode，OLED)具有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、结构轻薄以及柔性显示等优点，因此有着巨大的应用前景，吸引了众多研究者的关注。
在OLED中，起主导作用的发光客体材料是最重要的。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(IQE)只能达到25％，极大的限制了荧光电致发光器件的应用。另一种发光客体材料为重金属配合物磷光材料，其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，并且重金属配合物磷光发光材料在红光材料方面尚有待突破。其他发光客体材料如纯有机热活化延迟荧光(TADF)材料，可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(k RISC)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，具备上述条件的TADF 材料相对于重金属Ir配合物材料仍然属于少数，在磷光重金属材料有待突破的红光领域，TADF材料更是寥寥无几。
故，有必要提供一种红光热活化延迟荧光材料及有机发光二极管器件，以解决现有技术所存在的问题。
技术问题
目前具备快速的反向系间窜越常数(k RISC)以及高的光致发光量子产率(PLQY)的TADF材料相对于重金属Ir配合物材料仍然属于少数，在磷光重金属材料有待突破的红光领域，TADF材料更是寥寥无几，需要开发出更多且具备更优异性能的TADF材料。
技术解决方案
本发明的主要目的在于提供一种红光热活化延迟荧光材料及其制备方法，所述红光热活化延迟荧光材料具有优良的发光性能，包含一电子给体(D)部份与一电子受体(A)部份相结合的分子结构，可通过不同取代基来增加所述电子给体部份的给电子能力，使得所述红光热活化延迟荧光材料具有粉低的单三线态能级，实现红光发射。
本发明的另一目的在于提供一种有机发光二极管器件，包含上述红光热活化延迟荧光材料所形成的一发光材料层。
为达成本发明的前述目的，本发明一实施例提供一种红光热活化延迟荧光材料，其中所述红光热活化延迟荧光材料具有如下结构：
Figure PCTCN2019075305-appb-000001
其中X 1和X 2独立选自异丁基、甲氧基或二甲基氨基。
在本发明的一实施例中，所述红光热活化延迟荧光材料是
Figure PCTCN2019075305-appb-000002
本发明的另一实施例提供一种红光热活化延迟荧光材料的制备方法，包含步骤：(1)在一反应容器中置入一第一反应物及一第二反应物，其中所述第一反应物具有分子结构如下式(A)，所述第二反应物具有分子结构如下式(B)：
Figure PCTCN2019075305-appb-000003
Figure PCTCN2019075305-appb-000004
(2)将醋酸钯、三叔丁基膦四氟硼酸盐、叔丁醇钠及甲苯加入所述反应容器；以及
(3)在一惰性气体中加热至120℃以上以进行反应产出一红光热活化延迟荧光材料，所述红光热活化延迟荧光材料具有如下结构式(I)：
Figure PCTCN2019075305-appb-000005
其中Y是F、Cl或Br；X 1和X 2独立选自异丁基、甲氧基或二甲基氨基。
在本发明的一实施例中，所述惰性气体是氩气。
在本发明的一实施例中，所述第一反应物是
Figure PCTCN2019075305-appb-000006
Figure PCTCN2019075305-appb-000007
以及所述第二反应物是
Figure PCTCN2019075305-appb-000008
在本发明的一实施例中，所述红光热活化延迟荧光材料是
Figure PCTCN2019075305-appb-000009
本发明的再一实施例提供一种有机发光二极管器件，所述有机发光二极管器件包含：一透明基板；一透明导电层，设置于所述透明基板上；一空穴传输层，设置于所述透明导电层上；一发光材料层，设置于所述空穴传输层上；一电子传输层，设置于所述发光材料层上；以及一阴极层，设置于所述电子传输层上，其中所述发光材料层包含上述的红光热活化延迟荧光材料。
在本发明的一实施例中，所述透明导电层的材料为氧化铟锡。
在本发明的一实施例中，所述空穴传输层的材料是聚3,4-乙撑二氧噻吩：聚苯乙烯磺酸盐(PEDOT：PSS)。
在本发明的一实施例中，所述电子传输层的材料是1,3,5-三(3-(3-吡啶基)苯基)苯、1,3,5-三(1-苯基-1H-苯并咪唑-2-基)苯或3,3'-[5'-[3-(3-吡啶基)苯基][1,1':3',1”-三联苯]-3,3”-二基]二吡啶。
在本发明的一实施例中，所述发光材料层的厚度为15至20纳米。
在本发明的一实施例中，所述空穴传输层的厚度为40至50纳米。
在本发明的一实施例中，所述电子传输层的厚度为30至40纳米。
在本发明的一实施例中，所述有机发光二极管器件具有一最高亮度为1300至1800cd/m 2。
在本发明的一实施例中，所述有机发光二极管器件具有一最高电流效率为25至35cd/A。
有益效果
本发明实施例所提供的一种红光热活化延迟荧光材料及其制备方法，所述红光热活化延迟荧光材料具有优良的发光性能，包含一电子给体(D)部份与一电子受体(A)部份相结合的分子结构，可通过不同取代基来增加所述电子给体部份的给电子能力，使得所述红光热活化延迟荧光材料具有粉低的单三线态能级。
本发明的另一实施例提供一种有机发光二极管器件，包含上述红光热活化延迟荧光材料所形成的一发光材料层，实现红光发射。
附图说明
图1是本发明一实施例的一有机发光二极管器件的示意图。
图2是本发明的所述红光热活化延迟荧光材料(化合物1至3)在室温下的甲苯溶液中的光致发光光谱。
图3是本发明的所述红光热活化延迟荧光材料(化合物1至3)在室温下的甲苯溶液中的瞬态光致发光光谱。
本发明的实施方式
以下各实施例的说明是参考附加的图式，用以例示本发明可用以实施的特定实施例。再者，本发明所提到的方向用语，例如上、下、顶、底、前、后、左、右、内、外、侧面、周围、中央、水平、横向、垂直、纵向、轴向、 径向、最上层或最下层等，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。
本发明提供一种红光热活化延迟荧光材料，其中所述红光热活化延迟荧光材料具有如下结构：
Figure PCTCN2019075305-appb-000010
其中X 1和X 2独立选自异丁基、甲氧基或二甲基氨基。
所述红光热活化延迟荧光材料的制备方法包含步骤：(S1)在一反应容器中置入一第一反应物及一第二反应物，其中所述第一反应物具有分子结构如下式(A)，所述第二反应物具有分子结构如下式(B)：
Figure PCTCN2019075305-appb-000011
(S2)将醋酸钯、三叔丁基膦四氟硼酸盐、叔丁醇钠及甲苯加入所述反应容器；以及(S3)在一惰性气体中加热至120℃以上以进行反应产出一红光热活化延迟荧光材料，所述红光热活化延迟荧光材料具有如下结构式(I)：
Figure PCTCN2019075305-appb-000012
其中Y是F、Cl或Br；X 1和X 2独立选自异丁基、甲氧基或二甲基氨基。在本实施例中，所述惰性气体是氩气。
请参照图1，显示了本发明一实施例的一有机发光二极管器件的示意图。所述有机发光二极管器件主要包含一透明基板及一透明导电层所形成的一透明导电基板1、一空穴传输层2、一发光材料层3、一电子传输层4以及一阴极层5。所述透明导电层设置于所述透明基板上，所述透明导电层可例如是氧化铟锡(ITO)电极，然不限于此，一般所知的透明电极材料都可以采用。优选的，所述空穴传输层2的材料可例如是聚3,4-乙撑二氧噻吩：聚苯乙烯磺酸盐(PEDOT：PSS)，然不限于此。优选的，所述空穴传输层2的厚度小于50纳米，优选的是40至50纳米，可例如是50、45或40纳米，然不限于此。
在本发明的一实施例中，所述发光材料层3包含一红光热活化延迟荧光材料，其分子结构如下：
Figure PCTCN2019075305-appb-000013
其中X 1和X 2独立选自异丁基(-C(CH 3) 3)、甲氧基(-OCH 3)或二甲基 氨基(-N(CH 3) 2)。
优选的，所述红光热活化延迟荧光材料的具体结构如下式(1)至下式(3)：
Figure PCTCN2019075305-appb-000014
所述式(1)结构的合成路线及合成步骤如下：
Figure PCTCN2019075305-appb-000015
向100mL二口瓶中加入原料1(1.29g，5mmol)，3,6-二叔丁基吩噁嗪 (1.77g，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NaOt-Bu(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，旋成硅胶，柱层析(二氯甲烷:正己烷，v:v，1:2)分离纯化，得红色粉末2.1g，产率89％。 1H NMR(300MHz,CD 2Cl 2,δ):8.70(d,J＝6.3Hz,2H),8.39(d,J＝6.9Hz,2H),7.41(t,J＝7.2Hz,2H),7.00(s,2H),6.82-6.78(m,4H),1.27(s,18H).MS(EI)m/z:[M] +calcd for C 31H 30N 4O,474.24；found,474.19.Anal.Calcd for C 31H 30N 4O:C 78.45,H 6.39,N 11.81；found:C 78.37,H 6.27,N 11.62.
所述式(2)的合成路线及合成步骤如下：
Figure PCTCN2019075305-appb-000016
向100mL二口瓶中加入原料1(1.29g，5mmol)，3,6-二甲氧基吩噁嗪(1.46g，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NaOt-Bu(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，旋成硅胶，柱层析(二氯甲烷:正己烷，v:v，1:2)分离纯化，得红色粉末1.9g，产率90％。 1H NMR(300MHz,CD 2Cl 2,δ):8.70(d,J＝6.3Hz,2H),8.39(d,J＝6.9Hz,2H),7.41(t,J＝7.2Hz,2H),6.57(s,2H),6.51-6.43(m,4H),3.84(s,6H).MS(EI)m/z:[M] +calcd for C 25H 18N 4O 3,422.14；found,422.10.Anal.Calcd for C 25H 18N 4O 3:C 71.08,H 4.30,N 13.26；found:C 71.00,H 4.27,N 12.92.
所述式(3)的合成路线及合成步骤如下：
Figure PCTCN2019075305-appb-000017
向100mL二口瓶中加入原料1(1.29g，5mmol)，3,6-二N,N’二甲基吩噁嗪(1.61g，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NaOt-Bu(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，旋成硅胶，柱层析(二氯甲烷:正己烷，v:v，1:2)分离纯化，得红色粉末1.7g，产率76％。 1H NMR(300MHz,CD 2Cl 2,δ):8.70(d,J＝6.3Hz,2H),8.39(d,J＝6.9Hz,2H),7.41(t,J＝7.2Hz,2H),6.52-6.48(m,4H),4.37(s,2H),2.90(s,12H).MS(EI)m/z:[M] +calcd for C 27H 24N 6O,448.20found,448.19.Anal.Calcd for C 27H 24N 6O:C 72.30,H 5.39,N 18.74；found:C 72.17,H 5.27,N 18.62.
上述式(1)至式(3)的分子结构的电化学能级如下表1所示。
表1
Figure PCTCN2019075305-appb-000018
请参照图2，显示上述式(1)至式(3)的红光热活化延迟荧光材料在室温下甲苯溶液中的光致发光光谱。
请参照图3，显示上述式(1)至式(3)的红光热活化延迟荧光材料在室温下甲苯溶液中的瞬态光致发光光谱。
在一实施例中，所述发光材料层3的厚度小于20纳米，优选为15至20纳米，可例如是15、17或20纳米，然不限于此。
优选的，所述电子传输层4的材料是1,3,5-三(3-(3-吡啶基)苯基)苯 (Tm 3PyPB)、1,3,5-三(1-苯基-1H-苯并咪唑-2-基)苯(TPBI)或3,3'-[5'-[3-(3-吡啶基)苯基][1,1':3',1”-三联苯]-3,3”-二基]二吡啶(TmPyPB)。所述电子传输层4的厚度小于40纳米，优选为30至40纳米，可例如是30、35或40纳米，然不限于此。
在本发明的一实施例中，所述有机发光二极管器件具有一最高亮度为1300至1800cd/m 2(烛光/平方米)，优选为1465至1587cd/m 2。优选的，所述有机发光二极管器件具有一最高电流效率为25至35cd/A(烛光/安培)，优选为27.3至29.1cd/A。
使用本发明的上述式式(1)至式(3)的红光热活化延迟荧光材料作为一发光材料层，制作一有机发光二极管器件，具体方法为：在经过清洗的导电玻璃(ITO)衬底上依次旋涂，PESOT:PSS，然后在高真空条件下依次蒸镀本发明的所述红光热活化延迟荧光材料、Tm 3PyPB、1nm的LiF和100nm的Al。可获得如下表2所示的器件A1至A3。
表2
Figure PCTCN2019075305-appb-000019
接着，测量上述器件A1至A3的性能数据。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。测量结果如下表3。
表3
Figure PCTCN2019075305-appb-000020
从表3可知，本发明所提供的所述红光热活化延迟荧光材料式(1)至(3)所制成的有机发光二极管器件中，器件A3具有最高亮度为1587cd/m 2、最高电流效率为29.1cd/A，且最大外量子效率为21.6％。
本发明已由上述相关实施例加以描述，然而上述实施例仅为实施本发明的范例。必需指出的是，已公开的实施例并未限制本发明的范围。相反地，包含于权利要求书的精神及范围的修改及均等设置均包括于本发明的范围内。

Claims (12)

  1. 一种红光热活化延迟荧光材料，其中所述红光热活化延迟荧光材料具有如下结构：
    Figure PCTCN2019075305-appb-100001
    其中X 1和X 2独立选自异丁基、甲氧基或二甲基氨基。
  2. 如权利要求1所述的红光热活化延迟荧光材料，其中所述红光热活化延迟荧光材料是
    Figure PCTCN2019075305-appb-100002
  3. 一种有机发光二极管器件，其中所述有机发光二极管器件包含：
    一透明基板；
    一透明导电层，设置于所述透明基板上；
    一空穴传输层，设置于所述透明导电层上；
    一发光材料层，设置于所述空穴传输层上；
    一电子传输层，设置于所述发光材料层上；以及
    一阴极层，设置于所述电子传输层上，
    其中所述发光材料层包含如权利要求1所述的红光热活化延迟荧光材料。
  4. 如权利要求3所述的有机发光二极管器件，其中所述透明导电层的材料为氧化铟锡。
  5. 如权利要求3所述的有机发光二极管器件，其中所述空穴传输层的材料是聚3,4-乙撑二氧噻吩：聚苯乙烯磺酸盐。
  6. 如权利要求3所述的有机发光二极管器件，其中所述电子传输层的材料是1,3,5-三(3-(3-吡啶基)苯基)苯、1,3,5-三(1-苯基-1H-苯并咪唑-2-基)苯或3,3'-[5'-[3-(3-吡啶基)苯基][1,1':3',1”-三联苯]-3,3”-二基]二吡啶。
  7. 如权利要求3所述的有机发光二极管器件，其中所述发光材料层的厚度为15至20纳米；所述空穴传输层的厚度为40至50纳米；以及所述电子传输层的厚度为30至40纳米以下。
  8. 如权利要求3所述的有机发光二极管器件，其中所述有机发光二极管器件具有一最高亮度为1300至1800cd/m 2以及一最高电流效率为25至35cd/A。
  9. 一种红光热活化延迟荧光材料的制备方法，其特征在于；所述制备方法包含下列步骤：
    在一反应容器中置入一第一反应物及一第二反应物，其中所述第一反应物具有分子结构如下式(A)，所述第二反应物具有分子结构如下式(B)：
    Figure PCTCN2019075305-appb-100003
    Figure PCTCN2019075305-appb-100004
    将醋酸钯、三叔丁基膦四氟硼酸盐、叔丁醇钠及甲苯加入所述反应容器；以及
    在一惰性气体中加热至120℃以上以进行反应产出一红光热活化延迟荧光材料，所述红光热活化延迟荧光材料具有如下结构式(I)：
    Figure PCTCN2019075305-appb-100005
    其中Y是F、Cl或Br；X 1和X 2独立选自异丁基、甲氧基或二甲基氨基。
  10. 如权利要求9所述的红光热活化延迟荧光材料的制备方法，其中所述惰性气体是氩气。
  11. 如权利要求9所述的红光热活化延迟荧光材料的制备方法，其中所述第一反应物是
    Figure PCTCN2019075305-appb-100006
    Figure PCTCN2019075305-appb-100007
    以及所述第二反应物是
    Figure PCTCN2019075305-appb-100008
  12. 如权利要求9所述的红光热活化延迟荧光材料的制备方法，其中所述红光热活化延迟荧光材料是
    Figure PCTCN2019075305-appb-100009
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