WO2017101675A1 - 热活化延迟荧光材料及其在有机电致发光器件中的应用 - Google Patents

热活化延迟荧光材料及其在有机电致发光器件中的应用 Download PDF

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WO2017101675A1
WO2017101675A1 PCT/CN2016/107913 CN2016107913W WO2017101675A1 WO 2017101675 A1 WO2017101675 A1 WO 2017101675A1 CN 2016107913 W CN2016107913 W CN 2016107913W WO 2017101675 A1 WO2017101675 A1 WO 2017101675A1
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formula
organic electroluminescent
electroluminescent device
light
thermally activated
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PCT/CN2016/107913
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English (en)
French (fr)
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段炼
张东东
刘嵩
赵菲
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昆山国显光电有限公司
清华大学
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Priority to JP2018524282A priority Critical patent/JP2019501986A/ja
Priority to US15/770,730 priority patent/US10770661B2/en
Priority to KR1020187012736A priority patent/KR20180063264A/ko
Priority to EP16874732.7A priority patent/EP3369728B1/en
Publication of WO2017101675A1 publication Critical patent/WO2017101675A1/zh

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Definitions

  • the invention belongs to the field of materials, and in particular relates to a thermally activated delayed fluorescent material and its application in an organic electroluminescent device.
  • the organic light-emitting material mainly relies on an electron transition from an excited state to a ground state to generate light.
  • the luminescence generated by the electronic transition from the three-line excited state back to the ground state is extremely weak, and most of its energy is lost in the form of heat.
  • the luminescence is mainly generated by the electronic transition from the single-line excited state to the ground state, called electricity. Fluorescence. Since the probability of the three-line excited state is three times that of the single-line excited state, the equivalent of 75% of the energy is not used for luminescence. Making full use of this energy will effectively improve the luminous efficiency of the organic electroluminescent device.
  • Another method is to utilize the intersystem friction property of the lanthanoid compound, that is, to transfer the triplet energy of the luminescent layer host material to the 4f energy level of the lanthanide metal ion by energy transfer in the molecule, and then emit light, etc., but currently obtained
  • the device is inefficient.
  • Thermal activated delay fluorescent is a very popular scheme for utilizing triplet exciton energy.
  • TADF Thermal activated delay fluorescent
  • Adachi heat activated delayed fluorescent material
  • T 1 the difference ( ⁇ E ST) triplet level of such materials (T 1) with singlet level (S 1) it is small, the triplet energy can be It is transmitted to the singlet level and has been illuminated by fluorescent radiation.
  • ⁇ E ST triplet level of such materials
  • S 1 singlet level
  • the triplet energy can be It is transmitted to the singlet level and has been illuminated by fluorescent radiation.
  • the patent CN 102709485 A the device efficiency is improved by doping a fluorescent dye in a thermally delayed fluorescent body. In order to further improve the energy transfer recombination efficiency.
  • Adachi et al. in the article Nature communications 2014 "High-efficiency organic light-emitting diodes with fluorescent emitters", proposes to use a wide bandgap host doped TADF material as an auxiliary dye scheme.
  • a part of the energy is directly compounded on the main body, and the main body transfers the singlet energy to the dye.
  • the other part is compounded on the auxiliary dye.
  • the article reports on the structure and does not fully utilize the energy directly in the composite of the subject.
  • the common main material is used, the forbidden band width is large, and the required driving voltage is high.
  • the current TADF material has a short life problem, and one of the reasons is that the triplet lifetime is too long, and it is easy to generate exciton quenching due to processes such as TPA. Therefore, reducing the lifetime of the triplet excitons can effectively increase the lifetime of the TADF device.
  • the technical problem to be solved by the present invention is that the TADF material in the prior art has a problem of short life.
  • the present invention provides a novel TADF material which can improve the reverse intersystem crossing and intersystem of TADF material by heavy atom effect by introducing a heavy atom such as bromine or iodine into the original TADF molecule.
  • a heavy atom such as bromine or iodine
  • thermally activated delayed fluorescent material provided by the present invention is a compound having the general structure of Formula I or Formula II:
  • R1 is cyano
  • p is 1, 2 or 3
  • q is 1, 2 or 3
  • m is 1 or 2
  • n is 1 or 2.
  • Ar 1 is selected from a C 1-6 alkyl group, a methoxy group, an ethoxy group or a phenyl group substituted with one or more groups of a phenyl group,
  • Ar 2 and Ar 3 are selected from the following groups:
  • X is bromine or iodine.
  • the thermally activated delayed fluorescent material is a compound having the structure:
  • the present invention also provides the thermally activated delayed fluorescent material as a host material or luminescent dye application of the luminescent layer of an organic electroluminescent device.
  • the present invention further provides an organic electroluminescent device comprising a light-emitting layer comprising a host material and a luminescent dye doped in the host material, the luminescent dye being the thermally activated delayed fluorescent material described above.
  • the proportion of the luminescent dye in the luminescent layer is from 0.5% by weight to 10% by weight, more preferably 5% by weight.
  • the above organic electroluminescent device includes sequentially depositing an anode, a hole transporting layer, a light emitting layer, an electron transporting layer, and a cathode stacked on each other on a substrate.
  • a hole injection layer is further provided between the anode and the hole transport layer.
  • the present invention also provides an organic electroluminescent device comprising a light-emitting layer comprising a host material and a luminescent dye doped in the host material, the host material being the thermally activated delayed fluorescent material described above.
  • the proportion of the luminescent dye in the luminescent layer is from 1% by weight to 10% by weight.
  • the TADF material provided by the invention introduces heavy atoms such as bromine or iodine into the molecule, reduces the life of the TADF triplet state, and reduces the efficiency roll-off, thereby improving the life of the organic electroluminescent device.
  • Figure 1 is a schematic view showing the structure of an organic electroluminescent device of the present invention.
  • thermally activated delayed fluorescent material provided by the present invention is a compound having the general structure of Formula I or Formula II:
  • R 1 is cyano
  • p is 1, 2 or 3
  • q is 1, 2 or 3
  • m is 1 or 2
  • n is 1 or 2.
  • Ar 1 is selected from a C 1-6 alkyl group, a methoxy group, an ethoxy group or a phenyl group substituted with one or more groups of a phenyl group,
  • Ar 2 and Ar 3 is selected from the following groups:
  • X is bromine or iodine.
  • the thermally activated delayed fluorescent material of the present invention can reduce the triplet excitability by introducing a heavy atom such as bromine or iodine in the TADF molecule, thereby improving the reverse intersystem crossing and intersystem crossing of the TADF material by the heavy atom effect.
  • a heavy atom such as bromine or iodine
  • the life of the child ultimately increases the life of the device.
  • the thermally activated delayed fluorescent material of the present invention is a structural compound as follows.
  • the properties and preparation methods of each compound are as follows:
  • the molecular weight obtained by mass spectrometry was 615.97.
  • the molecular weight obtained by mass spectrometry was 1206.80.
  • the molecular weight obtained by mass spectrometry was 1142.89.
  • the molecular weight obtained by mass spectrometry was 1355.80.
  • the molecular weight obtained by mass spectrometry was 955.33.
  • the molecular weight obtained by mass spectrometry was 895.21.
  • the molecular weight obtained by mass spectrometry was 891.04.
  • the molecular weight obtained by mass spectrometry was 1313.93.
  • a method for synthesizing a structural compound represented by the formula (2-5) the reactant 3,6-dibromooxazolylbenzene is replaced with 3,7-dibromophenoxazinbenzene, and the same synthesis method as in the formula (2-1)
  • the compound of the formula (2-5) was obtained in a yield: 61%.
  • the molecular weight obtained by mass spectrometry was 986.87.
  • the molecular weight obtained by mass spectrometry was 1174.82.
  • the molecular weight obtained by mass spectrometry was 721.03.
  • the molecular weight obtained by mass spectrometry was 815.44.
  • the molecular weight obtained by mass spectrometry was 800.34.
  • the thermally activated delayed fluorescent material of the present invention can be used as a luminescent dye for the light-emitting layer of an organic electroluminescent device.
  • the organic electroluminescent device of the present invention comprises an anode 02, a hole injection layer 04, a hole transport layer 05, a light-emitting layer 06, an electron transport layer 07, and a cathode 03 which are sequentially stacked on a substrate 01. .
  • the material of the light-emitting layer 06 includes a host material and a luminescent dye doped in the host material.
  • the luminescent material is a compound having the structure of formula I or the structure of formula II.
  • the anode 02 may be an inorganic material or an organic conductive polymer.
  • the inorganic material is generally a metal oxide such as indium tin oxide (ITO), zinc oxide (ZnO) or indium zinc oxide (IZO) or a metal having a higher work function such as gold, copper or silver, preferably ITO;
  • the organic conductive polymer is preferably One of polythiophene/sodium polyvinylbenzenesulfonate (hereinafter referred to as PEDOT/PSS) and polyaniline (hereinafter referred to as PANI).
  • the cathode 03 is generally made of a metal having a lower work function such as lithium, magnesium, calcium, barium, aluminum or indium or an alloy thereof which is alternately formed with an alloy of copper, gold or silver or a metal and a metal fluoride.
  • the cathode is preferably a laminated LiF layer and an Al layer (the LiF layer is on the outer side).
  • the material of the hole transport layer 05 may be selected from the group consisting of aromatic amines and dendrite low molecular materials, preferably NPB.
  • the material of the electron transport layer 07 may be an organometallic complex (such as Alq 3 , Gaq 3 , BAlq or Ga (Saph-q)) or other materials commonly used for electron transport layers, such as aromatic fused rings (eg, pentacene, ruthenium). Or a compound of phenanthroline (such as Bphen, BCP).
  • organometallic complex such as Alq 3 , Gaq 3 , BAlq or Ga (Saph-q)
  • other materials commonly used for electron transport layers such as aromatic fused rings (eg, pentacene, ruthenium).
  • a compound of phenanthroline such as Bphen, BCP).
  • the organic electroluminescent device of the present invention may further have a hole injection layer 04 between the anode 02 and the hole transport layer 05, and the material of the hole injection layer 04 may be, for example, 4,4',4"-three ( 3-methylphenylaniline)triphenylamine is doped with F4TCNQ, or copper phthalocyanine (CuPc), or may be a metal oxide such as molybdenum oxide or cerium oxide.
  • a hole injection layer 04 between the anode 02 and the hole transport layer 05
  • the material of the hole injection layer 04 may be, for example, 4,4',4"-three ( 3-methylphenylaniline)triphenylamine is doped with F4TCNQ, or copper phthalocyanine (CuPc), or may be a metal oxide such as molybdenum oxide or cerium oxide.
  • each of the above layers may be conventionally used in the thickness of these layers in the art.
  • the present invention also provides a method of preparing the organic electroluminescent device, comprising sequentially depositing an anode 02, a hole injection layer 04, a hole transport layer 05, a light-emitting layer 06, an electron transport layer 07, and a cathode stacked on each other on a substrate 01. 03, then package.
  • the substrate may be a glass or a flexible substrate, and the flexible substrate may be a polyester-based, polyimide-based compound material or a thin metal sheet.
  • the lamination and encapsulation can take any suitable method known to those skilled in the art.
  • the present comparative example uses ITO (indium tin oxide) as the anode; NPB as the hole injection layer; TCTA as the hole transport layer; the light-emitting layer uses CBP as the host material, and DSA-Ph is the luminescent dye, which is doped in the light-emitting layer.
  • the mass percentage is 5 wt%); Bphen acts as an electron transport layer; LiF (5 nm) / Al acts as a cathode.
  • the structure is as follows:
  • the structure of this comparative example differs from that of Comparative Example 1 only in that the luminescent dye used in the luminescent layer is 2CzPN:
  • the structure of this example differs from Comparative Example 1 only in that the luminescent dye used in the luminescent layer is the compound 1-1 of the present invention:
  • the TADF material of Example 1 introduces heavy atoms, and the heavy atom effect enhances the reverse intersystem crossing and intersystem crossing of the TADF material, thereby reducing the lifetime of the triplet excitons and ultimately increasing the lifetime of the device.
  • Examples 2 to 5 differ from Example 1 only in that the doping concentration of the luminescent dye compound 1-1 in the light-emitting layer is different:
  • the current efficiency of the device is the highest when the doping concentration is 5wt%, and the voltage of the device is basically unchanged, but the lifetime of the device is The luminescent dye doping concentration increases and increases.
  • the OLED structure in this embodiment differs from Embodiment 1 only in that the luminescent layer is doped with a different compound having the structure of Formula I or Formula II as a luminescent dye:
  • the lifetime of the thermally activated delayed fluorescent material device containing the bromine or iodine heavy atom protected by the present invention is increased because the reverse intersystem crossing and intersystem of the TADF material are improved by the heavy atom effect.
  • the process of annihilation reduces the lifetime of the triplet excitons and ultimately increases the lifetime of the device.
  • the OLED structure in this embodiment differs from Example 1 in that the host material in the light-emitting layer is compound 2-2, and the luminescent dye is Ir(ppy) 3 .
  • Ir (ppy) 3 doping concentration is 1 ⁇ 10wt%.
  • the structure of this comparative example differs from Examples 7 to 9 only in that the host material used for the light-emitting layer is CBP:
  • the structure of this comparative example differs from Examples 7 to 9 only in that the host material used for the light-emitting layer is CC2TA:
  • the electrical properties of the device increased first and then decreased with the increase of the doping concentration of the luminescent dye, and the doping at 5 wt%
  • the concentration is optimal, but the device lifetime increases as the doping concentration of the dye increases.
  • the heat-activated delayed fluorescent material containing the bromine heavy atom protected by the present invention has a longer lifetime than that of the conventional host CBP (Comparative Example 3), and has the same structure but no heavy atomic heat.
  • Example 7 Compared with the device that activates the sensitized fluorescent material as the main component (Comparative Example 4), the electrical properties are not very different, but the device life of Example 7 is higher than that of Comparative Example 4, which is due to the heavy atom effect.
  • the inverse coefficient of the material Reduce the lifetime of triplet excitons and ultimately increase the lifetime of the device.

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Abstract

本发明公开了一种热活化延迟荧光材料及其在有机电致发光器件中的应用。该热活化延迟荧光材料为具有式Ⅰ或式Ⅱ通式结构的化合物：式Ⅰ和式Ⅱ中，R1为氰基，p为1,2或3，q为1,2或3，m为1或2，n为1或2， Ar1选自C1-6的烷基、甲氧基、乙氧基或苯基中一种以上的基团取代的苯基， Ar2和Ar3选自以下基团： X为溴或碘。本发明还公开了所述热活化延迟荧光材料作为有机电致发光器件的发光层的主体材料或发光染料的应用。

Description

热活化延迟荧光材料及其在有机电致发光器件中的应用 技术领域
本发明属于材料领域，具体涉及一种热活化延迟荧光材料及其在有机电致发光器件中的应用。
背景技术
在有机电致发光器件的电致发光过程中，主要依靠有机发光材料从激发态到基态的电子跃迁产生发光。在室温下，从三线激发态回到基态的电子跃迁产生的发光极微弱，其能量绝大部分以热的形式损失掉了，发光主要是由单线激发态到基态的电子跃迁产生，称为电致荧光。由于三线激发态产生的几率为单线激发态的三倍，因此相当于75％的能量没有被用于发光。充分利用这一能量，将有效地提高有机电致发光器件的发光效率。
为了充分利用发光层主体材料三线激发态的能量，人们曾提出过多种办法。例如研究和开发高效的磷光掺杂染料并掺杂于主体材料中，使得主体材料的三线态能量有效地传递给磷光掺杂染料，然后磷光掺杂染料产生磷光发光，从而使得发光层主体材料三线激发态的能量得到有效利用。该方法所获得的有机电致发光器件效率高，但材料合成需要铱、铂等贵重金属，价格昂贵。还有一种方法是利用镧系化合物的系间窜越性质，即利用分子内的能量转移将发光层主体材料的三线态能量转移至镧系金属离子的4f能级，然后发光等，但目前所得器件效率低。
热活化延迟荧光(TADF，Thermal active delay fluorescent)是目前非常热门的一种利用三线态激子能量的方案。例如，Adachi在其文章中报道了热活化延迟荧光材料，该类材料的三线态能级(T1)与单线态能级(S1)之差(ΔEST)较小，则三线态能量可以传输给单线态能级，并已荧光辐射发光。专利CN 102709485A中提到，通过在热延迟荧光主体中掺杂荧光染料来提高器件效率。为了进一步提高能量传输复合效率。Adachi等在文章Nature communications 2014“High-efficiency organic light-emitting diodes with fluorescent emitters”中，提出采用一种宽禁带主体掺杂TADF材料作为辅助染料方案。但在电荷复合过程中，一部分能量直接复合在主体上，主体将单线态能量传递给染料。另一部分在辅助染料上复合。文章报道结构，并不能完全有效利用直接在主体复合的能量。同时采用普通主体材料，禁带宽度大，所需驱动电压高。
但是，目前的TADF材料存在寿命较短的问题，原因之一是因为三线态寿命太长，容易产生TPA等过程造成激子的淬灭。因此，减小三线态激子的寿命可以有效地提高TADF器件的寿命。
技术问题
本发明要解决的技术问题是现有技术中的TADF材料存在寿命较短的问题。
技术解决方案
为了解决上述技术问题，本发明提供了一种新的TADF材料，其通过在原TADF分子中引入诸如溴或者碘等重原子，可以通过重原子效应提高TADF材料的反向系间窜越和系间窜越等过程从而减小三线态激子的寿命，最终提高器件的寿命。
本发明提供的热活化延迟荧光材料为具有式Ⅰ或式Ⅱ通式结构的化合物：
Figure PCTCN2016107913-appb-000001
式Ⅰ和式Ⅱ中，R1为氰基，p为1,2或3，q为1,2或3，m为1或2，n为1或2，
Ar1选自C1-6的烷基、甲氧基、乙氧基或苯基中一种以上的基团取代的苯基，
Ar2和Ar3选自以下基团：
Figure PCTCN2016107913-appb-000002
Figure PCTCN2016107913-appb-000003
X为溴或碘。
优选地，所述热活化延迟荧光材料为具有如下结构的化合物：
Figure PCTCN2016107913-appb-000004
Figure PCTCN2016107913-appb-000005
Figure PCTCN2016107913-appb-000006
Figure PCTCN2016107913-appb-000007
Figure PCTCN2016107913-appb-000008
本发明还提供所述热活化延迟荧光材料作为有机电致发光器件的发光层的主体材料或发光染料应用。
本发明另提供一种有机电致发光器件，包括发光层，所述发光层包括主体材料和掺杂在主体材料中的发光染料，所述发光染料为上述的热活化延迟荧光材料。优选地，所述发光染料在发光层中所占的比例为0.5wt％-10wt％，更优选为5wt％。
作为优选技术方案，上述的有机电致发光器件，包括在基板上依次沉积彼此层叠的阳极、空穴传输层、发光层、电子传输层及阴极。
优选地，所述阳极与空穴传输层之间还设有空穴注入层。
本发明还提供一种有机电致发光器件，包括发光层，所述发光层包括主体材料和掺杂在主体材料中的发光染料，所述主体材料为上述的热活化延迟荧光材料。
优选地，所述发光染料在发光层中所占的比例为1wt％-10wt％。
有益效果
本发明提供的TADF材料，其分子中引入诸如溴或者碘等重原子，减小TADF三线态寿命，减小效率滚降，从而提高有机电致发光器件的寿命。
附图说明
图1是本发明的有机电致发光器件的结构示意图。
本发明的实施方式
下面结合附图和具体实施例对本发明作进一步说明，以使本领域的技术人员可以更好的理解本发明并能予以实施，但所举实施例不作为对本发明的限定。
本发明提供的热活化延迟荧光材料，为具有式Ⅰ或式Ⅱ通式结构的化合物：
Figure PCTCN2016107913-appb-000009
Figure PCTCN2016107913-appb-000010
式Ⅰ和式Ⅱ中，R1为氰基，p为1,2或3，q为1,2或3，m为1或2，n为1或2，
Ar1选自C1-6的烷基、甲氧基、乙氧基或苯基中一种以上的基团取代的苯基，
Ar2和Ar3选自以下基团：
Figure PCTCN2016107913-appb-000011
Figure PCTCN2016107913-appb-000012
X为溴或碘。
本发明的热活化延迟荧光材料通过在TADF分子中引入诸如溴或者碘等重原子，可以通过重原子效应提高TADF材料的反向系间窜越和系间窜越等过程从而减小三线态激子的寿命，最终提高器件的寿命。
具体地，本发明的热活化延迟荧光材料为如下结构化合物，各化合物的性质及制备方法如下：
Figure PCTCN2016107913-appb-000013
式(1-1)，ΔEST＝0.16eV
其制备方法：
式(1-1)所示结构化合物合成方法：在氮气范围下，将3-溴咔唑(5mmol),溶于无水2mL THF中，然后加入氢化钠(5mmol)，混合物在室温下搅拌30分钟。随后，将1,2-二氰基-4,5-二氟基苯(1mmol)加入反应瓶中，继续搅拌1小时。最后将2mL冷水加入到混合物中将反应淬灭。待混合物冷却至室温后，通过真空抽滤，接着通过柱色谱提纯产物式(1-1)，将产物在真空中干燥。产率：75％。
质谱分析得到的分子量：615.97。
元素分析得到的各元素相对分子质量百分比：C：62.36；H：2.62；N：9.09；Br：25.93。
Figure PCTCN2016107913-appb-000014
式(1-2)，ΔEST＝0.14eV
其制备方法：
式(1-2)所示结构化合物合成方法：在氮气范围下，将3-溴吩噻嗪(10mmol),溶于无水4mL THF中，然后加入氢化钠(10mmol)，混合物在室温下搅拌30分钟。随后，将2,3,5,6-四氟基腈基苯(1mmol)加入反应瓶中，继续搅拌1小时。最后将2mL冷水加入到混合物中将反应淬灭。待混合物冷却至室温后，通过真空抽滤，接着通过柱色谱提纯产物式(1-2)，将产物在真空中干燥。产率：62％。
质谱分析得到的分子量：1206.80。
元素分析得到的各元素相对分子质量百分比：C：54.70；H：2.42；N：5.80；S：10.62；Br：26.46。
Figure PCTCN2016107913-appb-000015
式(1-3)，ΔEST＝0.13eV
其制备方法：
式(1-3)所示结构化合物合成方法：反应物3-溴吩噻嗪替换为3-溴吩噁嗪，经过与式(1-2)相同的合成方法，得式(1-3)所示结构化合物，产率：59％。
质谱分析得到的分子量：1142.89。
元素分析得到的各元素相对分子质量百分比：C：57.77；H：2.56；N：6.12；O：5.60；Br： 27.95。
Figure PCTCN2016107913-appb-000016
式(1-4)，ΔEST＝0.13eV
其制备方法：
式(1-4)所示结构化合物合成方法：反应物3-溴吩噻嗪替换为9-对碘苯吩嗪，经过与式(1-2)相同的合成方法，得式(1-4)所示结构化合物，产率：55％。
质谱分析得到的分子量：1631.03。
元素分析得到的各元素相对分子质量百分比：C：58.14；H：3.03；N：7.72；I：31.11。
Figure PCTCN2016107913-appb-000017
式(1-5)，ΔEST＝0.09eV
其制备方法：
式(1-5)所示结构化合物合成方法：在氮气范围下，将(1,1’-二对溴苯)对氨基苯(15mmol),溶于无水6mL THF中，然后加入氢化钠(15mmol)，混合物在室温下搅拌30分钟。随后，将2,4,6-四氟基-1,3,5-三氰基苯(1mmol)加入反应瓶中，继续搅拌1小时。最后将2mL冷水加入到混合物中将反应淬灭。待混合物冷却至室温后，通过真空抽滤，接着通过柱色谱提纯产物式(1-5)，将产物在真空中干燥。产率：31％。
质谱分析得到的分子量：1355.80。
元素分析得到的各元素相对分子质量百分比：C：55.78；H：2.68；N：6.20；Br：35.34。
Figure PCTCN2016107913-appb-000018
式(2-1)，ΔEST＝0.10eV
其制备方法：
式(2-1)所示结构化合物合成方法：在氮气范围下，将3,6-二溴咔唑基苯(10mmol),溶于无水4mL THF中，然后加入氢化钠(15mmol)，混合物在室温下搅拌30分钟。随后，将1-苯基-1,3,5-三嗪(1mmol)加入反应瓶中，继续搅拌1小时。最后将2mL冷水加入到混合物中将反应淬灭。待混合物冷却至室温后，通过真空抽滤，接着通过柱色谱提纯产物式(2-1)，将产物在真空中干燥。产率：49％。
质谱分析得到的分子量：955.33。
元素分析得到的各元素相对分子质量百分比：C：56.58；H：2.64；N：7.33；Br：33.46。
Figure PCTCN2016107913-appb-000019
式(2-2)，ΔEST＝0.15eV
其制备方法：
式(2-2)所示结构化合物合成方法：在氮气范围下，将对溴苯(5mmol),溶于无水4mL THF中，然后加入氢化钠(5mmol)，混合物在室温下搅拌30分钟。随后，将2,4-二(3-联咔唑)-6-氟基-1,3,5-三嗪(1mmol)加入反应瓶中，继续搅拌1小时。最后将2mL冷水加入到混合物中将反应淬灭。待混合物冷却至室温后，通过真空抽滤，接着通过柱色谱提纯产物式(2-2)，将产物在真空中干燥。产率：53％。
质谱分析得到的分子量：895.21。
元素分析得到的各元素相对分子质量百分比：C：76.34；H：3.82；N：10.93；Br：8.91。
Figure PCTCN2016107913-appb-000020
式(2-3)，ΔEST＝0.20eV
其制备方法：
式(2-3)所示结构化合物合成方法：在氮气范围下，将对碘苯(10mmol),溶于无水4mL THF中，然后加入氢化钠(10mmol)，混合物在室温下搅拌30分钟。随后，将2,4-二(3-联咔唑)-1,3,5-三嗪(1mmol)加入反应瓶中，继续搅拌1小时。最后将2mL冷水加入到混合物中将反应淬灭。待混合物冷却至室温后，通过真空抽滤，接着通过柱色谱提纯产物式(2-3)，将产物在真空中干燥。产率：53％。
质谱分析得到的分子量：891.04。
元素分析得到的各元素相对分子质量百分比：C：60.62；H：3.05；N：7.86；I：28.47。
Figure PCTCN2016107913-appb-000021
式(2-4)，ΔEST＝0.16eV
其制备方法：
式(2-4)所示结构化合物合成方法：在氮气范围下，将二对碘苯-4,4’-二连氨基苯(5mmol),溶于无水4mL THF中，然后加入氢化钠(5mmol)，混合物在室温下搅拌30分钟。随后，将4-氟基-2，6-苯基-1，3，5-三嗪(1mmol)加入反应瓶中，继续搅拌1小时。最后将2mL冷水加入到混合物中将反应淬灭。待混合物冷却至室温后，通过真空抽滤，接着通过柱色谱提纯产物式(2-4)，将产物在真空中干燥。产率：40％。
质谱分析得到的分子量：1313.93。
元素分析得到的各元素相对分子质量百分比：C：52.08；H：2.91；N：6.39；I：38.61。
Figure PCTCN2016107913-appb-000022
式(2-5)，ΔEST＝0.11eV
其制备方法：
式(2-5)所示结构化合物合成方法：反应物3,6-二溴咔唑基苯替换为3,7-二溴吩噁嗪苯，经过与式(2-1)相同的合成方法，得式(2-5)所示结构化合物，产率：61％。
质谱分析得到的分子量：986.87。
元素分析得到的各元素相对分子质量百分比：C：54.74；H：2.55；N：7.09；O：3.24；Br：32.37。
Figure PCTCN2016107913-appb-000023
式(2-6)，ΔEST＝0.05eV
其制备方法：
式(2-6)所示结构化合物合成方法：反应物3,6-二溴咔唑基苯替换为3,7-二溴吩噁嗪间苯，经过与式(2-1)相同的合成方法，得式(2-6)所示结构化合物，产率：61％。
质谱分析得到的分子量：1174.82。
元素分析得到的各元素相对分子质量百分比：C：45.99；H：2.14；N：5.96；O：2.72；I：43.19。
Figure PCTCN2016107913-appb-000024
式(2-7)，ΔEST＝0.16eV
其制备方法：
式(2-7)所示结构化合物合成方法：在氮气范围下，将二溴苯(10mmol)，溶于无水4mL THF中，然后加入氢化钠(10mmol)，混合物在室温下搅拌30分钟。随后，将2，4-二氟基-6-(11-苯基-11,12-二氢吲哚并[3,2b]咔唑基)-2，6-苯基-1，3，5-三嗪(1mmol)加入反应瓶中，继续搅拌1小时。最后将2mL冷水加入到混合物中将反应淬灭。待混合物冷却至室温后，通过真空抽滤，接着通过柱色谱提纯产物式(2-7)，将产物在真空中干燥。产率：34％。
质谱分析得到的分子量：721.03。
元素分析得到的各元素相对分子质量百分比：C：64.93；H：3.21；N：9.71；Br：22.15。
Figure PCTCN2016107913-appb-000025
式(2-8)，ΔEST＝0.16eV
其制备方法：
式(2-8)所示结构化合物合成方法：在氮气范围下，将6-苯基-2,9-二碘-吲哚并[2,3a]咔唑(10mmol),溶于无水4mL THF中，然后加入氢化钠(10mmol)，混合物在室温下搅拌30分钟。随后，将6-氟基-2，4-二苯基-1，3，5-三嗪(1mmol)加入反应瓶中，继续搅拌1小时。最后将2mL冷水加入到混合物中将反应淬灭。待混合物冷却至室温后，通过真空抽滤，接着通过柱色谱提纯产物式(2-8)，将产物在真空中干燥。产率：31％。
质谱分析得到的分子量：815.44。
元素分析得到的各元素相对分子质量百分比：C：57.44；H：2.84；N：8.59；I：31.13。
Figure PCTCN2016107913-appb-000026
式(2-9)，ΔEST＝0.17eV
其.制备方法：
式(2-9)所示结构化合物合成方法：在氮气范围下，将11-对溴苯基-吲哚并[2,3a]咔唑(7mmol),溶于无水4mL THF中，然后加入氢化钠(10mmol)，混合物在室温下搅拌30分钟。随后，将6-氟基-2，4-二对溴苯基-1，3，5-三嗪(1mmol)加入反应瓶中，继续搅拌1小时。最后将2mL冷水加入到混合物中将反应淬灭。待混合物冷却至室温后，通过真空抽滤，接着通过柱色谱提纯产物 式(2-9)，将产物在真空中干燥。产率：36％。
质谱分析得到的分子量：800.34。
元素分析得到的各元素相对分子质量百分比：C：58.53；H：2.77；N：8.75；Br：29.95。
本发明的热活化延迟荧光材料可用作有机电致发光器件发光层的发光染料。
如图1所示，本发明的有机电致发光器件包括在基板01上依次沉积彼此层叠的阳极02、空穴注入层04、空穴传输层05、发光层06、电子传输层07及阴极03。
其中发光层06的材料包括主体材料和掺杂在主体材料中的发光染料，
发光材料为具有式Ⅰ结构或式Ⅱ结构的化合物。
本发明的有机发光显示器件实施例：阳极02可以采用无机材料或有机导电聚合物。无机材料一般为氧化铟锡(ITO)、氧化锌(ZnO)、氧化铟锌(IZO)等金属氧化物或金、铜、银等功函数较高的金属，优选ITO；有机导电聚合物优选为聚噻吩/聚乙烯基苯磺酸钠(以下简称PEDOT/PSS)、聚苯胺(以下简称PANI)中的一种。
阴极03一般采用锂、镁、钙、锶、铝、铟等功函数较低的金属或它们与铜、金、银的合金，或金属与金属氟化物交替形成的电极层。本发明中阴极优选为层叠的LiF层和Al层(LiF层在外侧)。
空穴传输层05的材料可以选自芳胺类和枝聚物类低分子材料，优选NPB。
电子传输层07的材料可采用有机金属配合物(如Alq3、Gaq3、BAlq或Ga(Saph-q))或其他常用于电子传输层的材料，如芳香稠环类(如pentacene、苝)或邻菲咯啉类(如Bphen、BCP)化合物。
本发明的有机电致发光器件还可在阳极02和空穴传输层05之间具有空穴注入层04，所述空穴注入层04的材料例如可采用4,4',4”-三(3-甲基苯基苯胺)三苯胺掺杂F4TCNQ，或者采用铜酞菁(CuPc)，或可为金属氧化物类，如氧化钼，氧化铼。
上述各层的厚度可采用本领域中这些层常规的厚度。
本发明还提供所述有机电致发光器件的制备方法，包括在基板01上依次沉积彼此层叠的阳极02、空穴注入层04、空穴传输层05、发光层06、电子传输层07及阴极03，然后封装。
基板可以是玻璃或是柔性基片，所述柔性基片可采用聚酯类、聚酰亚胺类化合物材料或者薄金属片。所述层叠及封装可采用本领域技术人员已知的任意合适方法。
对比例1：
本对比例以ITO(氧化铟锡)作为阳极；以NPB作为空穴注入层；以TCTA作为空穴传输层；发光层采用CBP作为主体材料，DSA-Ph为发光染料，在发光层中掺杂的质量百分比为5wt％)；Bphen作为电子传输层；LiF(5nm)/Al作为阴极。结构如下：
ITO/NPB(40nm)/TCTA(10nm)/CBP:5wt％DSA-Ph(30nm)/Bphen(40nm)/LiF(5nm)/Al
Figure PCTCN2016107913-appb-000027
对比例2：
本对比例的结构与对比例1的区别仅在于发光层采用的发光染料为2CzPN：
ITO/NPB(40nm)/TCTA(10nm)/CBP:5wt％2CzPN(30nm)/Bphen(40nm)/LiF(5nm)/Al
Figure PCTCN2016107913-appb-000028
实施例1
本实施例的结构与对比例1的区别仅在于发光层采用的发光染料为本发明的化合物1-1：
Figure PCTCN2016107913-appb-000029
ITO/NPB(40nm)/TCTA(10nm)/CBP:5wt％化合物1-1(30nm)/Bphen(40nm)/LiF(5nm)/Al
Figure PCTCN2016107913-appb-000030
实施例1的TADF材料由于引入了重原子，重原子效应提高TADF材料的反向系间窜越和系间窜越等过程从而减小三线态激子的寿命，最终提高器件的寿命。
实施例2～5
实施例2～5的结构与实施例1的区别仅在于发光层中发光染料化合物1-1掺杂浓度不同：
ITO/NPB(40nm)/TCTA(10nm)/CBP:0.5～10wt％化合物1-1(30nm)/Bphen(40nm)/LiF(5nm)/Al设计不同的掺杂浓度实施例
Figure PCTCN2016107913-appb-000031
从上表看出，发光染料浓度的增加导致了器件的电流效率先增后减，在掺杂浓度为5wt％时器件的电流效率最高，器件的电压基本无明显改变，但器件的寿命随着发光染料掺杂浓度的提高而增加。
实施例6
本实施例中的OLED结构与实施例1的区别仅在于发光层中掺杂不同的具有式Ⅰ或式Ⅱ结构的化合物作为发光染料：
ITO/NPB(40nm)/TCTA(10nm)/CBP:5wt％(具有式Ⅰ或式Ⅱ结构的化合物)(30nm)/Bphen(40nm)/LiF(5nm)/Al
Figure PCTCN2016107913-appb-000032
从上表看出，本发明所保护的含有的溴或碘重原子的热活化延迟荧光材料器件寿命均增加了，这是因为通过重原子效应提高TADF材料的反向系间窜越和系间窜越等过程从而减小三线态激子的寿命，最终提高器件的寿命。
实施例7～9
本实施例中的OLED结构与实施例1的区别在于发光层中的主体材料为化合物2-2，发光染料为Ir(ppy)3。Ir(ppy)3掺杂浓度(在发光层中所占的重量百分比)为1～10wt％。
ITO/NPB(40nm)/TCTA(10nm)/化合物2-2:1～10wt％Ir(ppy)3(30nm)/Bphen(40nm)/LiF(5nm)/Al。
对比例3
本对比例的结构与实施例7～9的区别仅在于发光层采用的主体材料为CBP：
ITO/NPB(40nm)/TCTA(10nm)/CBP:5wt％Ir(ppy)3(30nm)/Bphen(40nm)/LiF(5nm)/Al。
对比例4
本对比例的结构与实施例7～9的区别仅在于发光层采用的主体材料为CC2TA：
Figure PCTCN2016107913-appb-000033
Figure PCTCN2016107913-appb-000034
从上表看出，对比三种不同掺杂浓度的实施例7，实施例8和实施例9，器件的电学性能随发光染料的掺杂浓度的提高先升后降，在5wt％的掺杂浓度时达到最优，但是器件寿命随染料的掺杂浓度的提高而提高。另外，本发明所保护的含有的溴重原子的热活化延迟荧光材料做主体的器件寿命均比传统主体CBP做主体的器件(对比例3)寿命高，与相同结构但是不带重原子的热活化敏化荧光材料做主体的器件(对比例4)对比，电学性能并没有很大区别，但是实施例7的器件寿命比对比例4的器件寿命要高，这是由于重原子效应提高了TADF材料的反向系间窜越系数，从而 减小三线态激子的寿命，最终提高器件的寿命。
以上所述实施例仅是为充分说明本发明而所举的较佳的实施例，本发明的保护范围不限于此。本技术领域的技术人员在本发明基础上所作的等同替代或变换，均在本发明的保护范围之内。本发明的保护范围以权利要求书为准。

Claims (10)

  1. 一种热活化延迟荧光材料，其特征在于，所述热活化延迟荧光材料为具有式Ⅰ或式Ⅱ通式结构的化合物：
    Figure PCTCN2016107913-appb-100001
    式Ⅰ和式Ⅱ中，R1为氰基，p为1,2或3，q为1,2或3，m为1或2，n为1或2，
    Ar1选自C1-6的烷基、甲氧基、乙氧基或苯基中一种以上的基团取代的苯基，
    Ar2和Ar3选自以下基团：
    Figure PCTCN2016107913-appb-100002
    Figure PCTCN2016107913-appb-100003
    X为溴或碘。
  2. 根据权利要求1所述的热活化延迟荧光材料，其特征在于，所述热活化延迟荧光材料为具有如下结构的化合物：
    Figure PCTCN2016107913-appb-100004
    Figure PCTCN2016107913-appb-100005
    Figure PCTCN2016107913-appb-100006
    Figure PCTCN2016107913-appb-100007
    Figure PCTCN2016107913-appb-100008
  3. 权利要求1或2所述的热活化延迟荧光材料的应用，其特征在于，所述热活化延迟荧光材料作为有机电致发光器件的发光层的主体材料或发光染料应用。
  4. 一种有机电致发光器件，包括发光层，其特征在于，所述发光层包括主体材料和掺杂在主体材料中的发光染料，所述发光染料为权利要求1或2所述的热活化延迟荧光材料。
  5. 根据权利要求4所述的有机电致发光器件，其特征在于，所述发光染料在发光层中所占的比例为0.5wt％-10wt％。
  6. 根据权利要求5所述的有机电致发光器件，其特征在于，所述发光染料在发光层中所占的比例为5wt％。
  7. 根据权利要求4所述的有机电致发光器件，其特征在于，包括在基板上依次沉积彼此层叠的阳极、空穴传输层、发光层、电子传输层及阴极。
  8. 根据权利要求7所述的有机电致发光器件，其特征在于，所述阳极与空穴传输层之间还设有空穴注入层。
  9. 一种有机电致发光器件，包括发光层，其特征在于，所述发光层包括主体材料和掺杂在主体材料中的发光染料，所述主体材料为权利要求1或2所述的热活化延迟荧光材料。
  10. 根据权利要求9所述的有机电致发光器件，其特征在于，所述发光染料在发光层中所占的比例为1wt％-10wt％。
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