CN112142717B - 一种热激活延迟荧光材料及其应用 - Google Patents
一种热激活延迟荧光材料及其应用 Download PDFInfo
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Abstract
本发明属于有机电致发光器件技术领域,特别涉及一种热激活延迟荧光材料及其应用。本发明所提供的热激活延迟荧光材料具有双喹喔啉结构,结构新颖,具有良好的光电性能,适合作为有机电致发光器件的发光材料,采用所述发光材料制备得到的有机电致发光器件具有更高的器件效率和使用寿命,同时,本发明所述热激活延迟荧光材料具有非常好的热稳性和成膜性,玻璃化转变温度高达215℃,因此具有良好的热稳定性。
Description
技术领域
本发明属于有机电致发光器件技术领域,特别涉及一种热激活延迟荧光材料及其应用。
背景技术
有机电致发光器件(OLEDs)为在两个金属电极之间通过旋涂或者真空蒸镀沉积一层有机材料制备而成的器件,一个经典的三层有机电致发光器件包含空穴传输层、发光层和电子传输层,由阳极产生的空穴经空穴传输层跟由阴极产生的电子经电子传输层结合在发光层形成激子,而后发光。有机电致发光器件可以根据需要通过改变发光层的材料来调节发射各种需要的光。
有机电致发光器件作为一种新型的显示技术,具有自发光、宽视角、低能耗、效率高、薄、色彩丰富、响应速度快、适用温度范围广、低驱动电压、可制作柔性可弯曲与透明的显示面板以及环境友好等独特优点,可以应用在平板显示器和新一代照明上,也可以作为LCD的背光源。
热激活延迟荧光材料(TADF,thermally activated delayed fluorescence)是一种新型的有机发光材料,其发光原理是三线态T1激子在热激活作用下反向系间窜越生成单线态S1激子,获得100%单线态激子,进而辐射跃迁产生荧光,既避免了使用昂贵的重金属配合物,且器件效率可与磷光器件相媲美。由于无需金属配合物,所以TADF材料具有价格低廉、环境友好等优点,使得在OLED、生物等领域具有广阔应用前景。
从2009年TADF材料发明以来,已经取得了快速发展,但是,现有的TADF材料及其OLED器件还是存在很多不足,特别是材料的稳定性、器件的稳定性和使用寿命。因此,开发高效稳定的TADF材料具有重要意义。根据TADF的特性,匹配的HOMO能级和LUMO能级能够降低分子内电子云的重叠,并且可以通过在推电子基团和吸电子基团中间加入阻隔基团来实现电子云的分离,降低分子的三重态激发态和单重态激发态之间的能级差,提高发光效率和降低电压。
另外,相比较传统的荧光材料,TADF材料的稳定性存在不足,效率滚降比较厉害,因此,需要开发具有高稳定性和高效率的热激活延迟荧光材料。
发明内容
本发明的目的在于解决现有技术问题,提供一种热激活延迟荧光材料及其应用,所述材料具有良好的热稳定性,并以此材料制备的有机电致发光器件具有更高的效率、更低的工作电压和更长的使用寿命。
本发明解决其技术问题所采用的技术方案是:
本发明的目的之一在于提供一种热激活延迟荧光材料,所述材料结构如式I所示:
其中,L1和L3各自独立地表示为空、单键、O、S、Se、NAr、CR1R2,Ar表示为C6-C30取代或者未取代的芳基,R1和R2各自独立地表示为C1-C12取代或者未取代烷基、C6-C30取代或者未取代的芳基;
L2表示为C6-C30取代或未取代的芳基、C3-C30取代或未取代的杂芳基之一;
Ar1-Ar4各自独立地表示为C6-C30取代或者未取代的芳基。
优选的,所述Ar为苯基。
优选的,所述R1和R2各自独立地表示为甲基、苯基、甲苯基之一。
优选的,所述L2为苯基、吡啶基、嘧啶基、萘基、联苯基、吡嗪基、哒嗪基、三氟甲基苯基、氰基苯基之一。
优选的,所述Ar1-Ar4各自独立地表示为苯基、甲苯基、叔丁基苯基、芴基、二苯并呋喃基、二苯并噻吩基、苯基咔唑基之一。
优选的,所述热激活延迟荧光材料为如下化合物中的任意一种:
本发明的目的之二在于提供一种有机电致发光器件,所述有机致电发光器件包含阳极、阴极和有机层,所述有机层包含发光层,以及空穴注入层、空穴传输层、空穴阻挡层、电子注入层、电子传输层中的一层或一层以上,其中所述发光层含有如结构式I所述的热激活延迟荧光材料。
优选的,所述热激活延迟荧光材料用作发光层中的客体材料、主体材料中的任意一种。
与现有技术相比,本发明的有益效果是:本发明的TADF材料结构新颖,具有良好的光电性能,适合作为有机电致发光器件的发光材料,采用所述发光材料的有机电致发光器件具有更高的器件效率和使用寿命,同时,本发明所述热激活延迟荧光材料具有非常好的热稳性和成膜性,玻璃化转变温度高达215℃,因此具有良好的热稳定性。
附图说明
图1为本发明的一种有机电致发光器件结构示意图。
图中:110、玻璃基板,120、阳极,130、空穴注入层,140、空穴传输层,150、发光层,160、空穴阻挡层,170、电子传输层,180、电子注入层,190、阴极。
具体实施方式
下面通过具体实施例,并结合附图,对本发明的技术方案作进一步的具体说明。
本发明的目的之一在于提供一种热激活延迟荧光材料,所述材料结构如式I所示:
其中,L1和L3各自独立地表示为空、单键、O、S、Se、NAr、CR1R2,Ar表示为C6-C30取代或者未取代的芳基,R1和R2各自独立地表示为C1-C12取代或者未取代烷基、C6-C30取代或者未取代的芳基;
L2表示为C6-C30取代或未取代的芳基、C3-C30取代或未取代的杂芳基之一;
Ar1-Ar4各自独立地表示为C6-C30取代或者未取代的芳基。
本发明中,所述Ar为苯基。
本发明中,所述R1和R2各自独立地表示为甲基、苯基、甲苯基之一。
本发明中,所述L2为苯基、吡啶基、嘧啶基、萘基、联苯基、吡嗪基、哒嗪基、三氟甲基苯基、氰基苯基之一。
本发明中,所述Ar1-Ar4各自独立地表示为苯基、甲苯基、叔丁基苯基、芴基、二苯并呋喃基、二苯并噻吩基、苯基咔唑基之一。
本发明中,所述热激活延迟荧光材料为如下化合物中的任意1种:
本发明的目的之二在于提供一种有机电致发光器件,所述有机电致发光器件包含阳极、阴极和有机层,所述有机层包含发光层,以及空穴注入层、空穴传输层、空穴阻挡层、电子注入层、电子传输层中的一层或一层以上,其中发光层含有如结构式I所述的热激活延迟荧光材料。
本发明中,所述热激活延迟荧光材料用作发光层中的客体材料、主体材料中的任意一种。
本发明中,所述有机层中的发光层含有如结构式I所述的热激活延迟荧光材料。
本发明提供了若干个示例性的化合物。在随后的具体实施例中,对部分化合物的合成方法进行示例性的描述,并对相应化合物制备的有机电致发光器件进行示例性描述,但本发明的保护范围绝不仅限于此。
实施例中间体的制备
1.中间体I的合成
在烧瓶中加入5,8-二溴-2,3-二苯基喹喔啉(10g,22.7mmol),咔唑(3.4g,20.3mmol),叔丁醇钠(3.3g,34.3mmol),Pd2(dba)3(0.15g),三叔丁基膦(0.1g)和100mL无水甲苯,回流反应2小时,加稀盐酸调至弱酸性分液,干燥,浓缩,粗品经甲苯重结晶得到7.2g,产率为60%。1H NMR(400MHz,CDCl3)δ:8.11-8.14(m,2H),8.04(d,J=7.2Hz,1H),7.82(d,J=7.6Hz,1H),7.61-7.63(m,2H),7.50-7.57(m,4H),7.32-7.38(m,8H),7.20-7.24(m,2H).HRMS(ESI,m/z):[M+H]+526.10.
2.中间体II的合成
在烧瓶中加入中间体I(7g,13.3mmol),联硼酸频哪酯(4.1g,16.1mmol),醋酸钾(3.9g,39.7mmol),Pd(PPh3)3Cl2(0.07g),70mL无水甲苯,回流反应5小时,冷却,过硅胶,甲苯淋洗,浓缩至约30mL,滴加30mL乙醇析晶,过滤,烘干,得到7.1g类白色产品,产率为93%。1H NMR(400MHz,CDCl3)δ:8.10-8.13(m,2H),7.91(d,J=7.2Hz,1H),7.63-7.65(m,2H),7.52-7.58(m,5H),7.39-7.43(m,2H),7.32-7.38(m,6H),7.22-7.26(m,2H),1.24(s,12H).HRMS(ESI,m/z):[M+H]+574.25.
3.中间体III的合成
在烧瓶中加入5,8-二溴-2,3-二苯基喹喔啉(10g,22.7mmol),9,9-二甲基-9,10-二氢吖啶(4.3g,20.5mmol),叔丁醇钠(3.3g,34.3mmol),Pd2(dba)3(0.15g),三叔丁基膦(0.1g)和100mL无水甲苯,回流反应2小时,加稀盐酸调至弱酸性分液,干燥,浓缩,粗品经甲苯重结晶得到8g白色产品,产率为62%。1H NMR(400MHz,CDCl3)δ:8.01(d,J=8.0Hz,1H),7.51-7.61(m,5H),7.31-7.39(m,6H),7.11-7.21(m,6H),7.00-7.02(m,2H),1.53(s,6H).HRMS(ESI,m/z):[M+H]+561.12.
4.中间体IV的合成
在烧瓶中加入中间体III(7g,12.3mmol),联硼酸频哪酯(3.75g,14.8mmol),醋酸钾(3.6g,36.7mmol),Pd(PPh3)3Cl2(0.07g),70mL无水甲苯,回流反应5小时,冷却,过硅胶,甲苯淋洗,浓缩至约30mL,滴加30mL乙醇析晶,过滤,烘干,得到6.9g类白色产品,产率为91%。1H NMR(400MHz,CDCl3)δ:7.85(d,J=7.6Hz,1H),7.54-7.60(m,4H),7.41(d,J=7.2Hz,1H),7.34-7.38(m,6H),7.17-7.21(m,4H),7.09-7.13(m,2H),7.00-7.03(m,2H),1.53(s,6H),1.24(s,12H).HRMS(ESI,m/z):[M+H]+616.33.
实施例1化合物1的合成
在烧瓶中加入中间体II(2.0g,3.49mmol),1,4-二溴苯(0.40g,1.70mmol),碳酸钾(0.70g,5.09mmol),Pd(PPh3)4(0.01g),再加入甲苯(10mL),乙醇(5mL)和去离子水(5mL),氮气保护下回流反应5小时,分液,浓缩,粗品经柱色谱得到1.4g白色产品,产率为86%。1HNMR(400MHz,CDCl3)δ:8.11-8.14(m,4H),7.93(d,J=6.4Hz,2H),7.79(d,J=6.4Hz,2H),7.53-7.59(m,12H),7.47-7.49(m,4H),7.30-7.37(m,16H),7.19-7.24(m,4H).HRMS(ESI,m/z):[M+H]+969.35.
实施例2化合物9的合成
在烧瓶中加入中间体II(2g,3.49mmol),2,5-二溴吡啶(0.40g,1.69mmol),碳酸钾(0.70g,5.06mmol),Pd(PPh3)4(0.01g),再加入甲苯(10mL),乙醇(5mL)和去离子水(5mL),氮气保护下回流反应5小时,分液,浓缩,粗品经柱色谱得到1.3g白色产品,产率为80%。1HNMR(400MHz,CDCl3)δ:9.43(d,J=2.0Hz,1H),8.07-8.14(m,6H),7.94(d,J=6.8Hz,1H),7.80-7.88(m,3H),7.54-7.59(m,8H),7.47-7.49(m,4H),7.30-7.37(m,16H),7.19-7.24(m,4H).HRMS(ESI,m/z):[M+H]+970.35.
实施例3化合物8的合成
在烧瓶中加入中间体IV(2g,3.25mmol),1,4-二溴苯(0.37g,1.57mmol),碳酸钾(0.65g,4.70mmol),Pd(PPh3)4(0.01g),再加入甲苯(10mL),乙醇(5mL)和去离子水(5mL),氮气保护下回流反应5小时,分液,浓缩,粗品经柱色谱得到1.4g白色产品,产率为85%。1HNMR(400MHz,CDCl3)δ:.7.89(d,J=7.2Hz,2H),7.50-7.59(m,14H),7.30-7.37(m,12H),7.20-7.24(m,8H),7.10-7.15(m,4H),6.97-6.99(m,4H),1.56(s,12H).HRMS(ESI,m/z):[M+H]+1053.44.
实施例4化合物23的合成
在烧瓶中加入中间体IV(2g,3.25mmol),1,3-二溴苯(0.37g,1.57mmol),碳酸钾(0.65g,4.70mmol),Pd(PPh3)4(0.01g),再加入甲苯(10mL),乙醇(5mL)和去离子水(5mL),氮气保护下回流反应5小时,分液,浓缩,粗品经柱色谱得到1.4g白色产品,产率为85%。1HNMR(400MHz,CDCl3)δ:8.25(t,J=1.6Hz,1H),7.89(d,J=7.2Hz,2H),7.54-7.59(m,9H),7.49(d,J=7.6Hz,2H),7.40-7.43(m,2H),7.30-7.36(m,12H),7.20-7.23(m,8H),7.10-7.15(m,4H),6.97-6.99(m,4H),1.56(s,12H).HRMS(ESI,m/z):[M+H]+1053.47.
实施例5化合物25的合成
在烧瓶中加入中间体IV(2g,3.25mmol),2,6-二溴吡啶(0.375g,1.58mmol),碳酸钾(0.6g,4.78mmol),Pd(PPh3)4(0.01g),再加入甲苯(10mL),乙醇(5mL)和去离子水(5mL),氮气保护下回流反应5小时,分液,浓缩,粗品经柱色谱得到1.4g白色产品,产率为84%。1HNMR(400MHz,CDCl3)δ:8.25(t,J=1.6Hz,1H),7.89(d,J=7.2Hz,2H),7.54-7.59(m,9H),7.49(d,J=7.6Hz,2H),7.40-7.43(m,2H),7.30-7.36(m,12H),7.20-7.23(m,8H),7.10-7.15(m,4H),6.97-6.99(m,4H),1.56(s,12H).HRMS(ESI,m/z):[M+H]+1054.45.
试验例1实施例1-5的化合物玻璃化转化温度的测试
用差示扫描量热仪Pyris Diamond(DSC 2920)在氮气保护下,以10℃/分钟的加热和冷却速度分别测试实施例1-5制备得到的化合物的玻璃化转变温度(Tg),并以化合物EM1作为对比例1进行对比。具体如表1所示。
化合物EM1的结构式如下所示:
表1各化合物的玻璃化转变温度
化合物 | 玻璃化温度(℃) | |
实施例1 | 1 | 198 |
实施例2 | 9 | 207 |
实施例3 | 8 | 211 |
实施例4 | 23 | 225 |
实施例5 | 25 | 237 |
对比例1 | EM1 | 134 |
从表1可以看出,本发明的化合物的玻璃化温度明显高于对比例1已经公开的化合物EM1,说明本发明采用两个喹喔啉作为吸电子基团可以有效地改善有机电致发光材料的热稳定性。
实施例6-10有机电致发光器件的制备
本发明中得到的TADF化合物可以作为发光客体材料用在有机电致发光器件上,为进一步说明本发明得到的TADF材料的应用,采用本发明实施例1-5的化合物并通过以下方法制备对应的OLED器件:
a.将带有阳极120的透明导电ITO玻璃基板110(中国南玻集团股份有限公司)依次经:去离子水,乙醇,丙酮和去离子水洗净,再用氧等离子处理30秒;
b.在ITO上蒸镀3nm厚的MnO3(氧化钼)为空穴注入层130;
c.在空穴注入层上蒸镀50nm厚的TAPC为空穴传输材料140;
d.蒸镀TCTA,形成5nm厚的电子阻挡层150;
e.在电子阻挡层上蒸镀20nm厚的发光层160,发光层160中,以85%重量比的CBP作为主体材料,本发明化合物为客体材料;
f.在发光层上蒸镀40nm厚的BmPYPB作为电子传输层170;
g.蒸镀1nm LiF为电子注入层180和80nm Al作为器件阴极190。
采用本发明实施例1-5的化合物作为发光层客体发光材料所制备的器件(结构示意图见图1)测得的在100cd/m2的亮度下的器件性能如表2。
对比例2对比有机电致发光器件的制备
对比例2所述器件的制备方法同实施例6-10器件的制备方法,其中采用EM1代替本发明化合物作为发光客体材料。
试验例2实施例6-10的有机电致发光器件性能测试
对实施例6-10制备得到的有机电致发光器件在100cd/m2的亮度下进行性能测试,并与对比例2制备得到的对比有机电致发光器件进行对比,测试结果见表2。
其中,器件制备过程中中涉及化合物的结构式如下:
从表2中可以看出,本发明制备得到的热激活延迟荧光材料用于有机电致发光器件,可以降低工作电压,提高器件效率,是具有优良性能的TADF材料。
综上所述,本发明的化合物具有高的稳定性,同时制备的有机电致发光器件具有高的效率和光纯度。
以上所述的实施例只是本发明的较佳方案,并非对本发明作任何形式上的限制,在不超出权利要求所记载的技术方案的前提下还有其它的变体及改型。
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009170818A (ja) * | 2008-01-18 | 2009-07-30 | Mitsui Chemicals Inc | キノキサリン誘導体、およびそれを含む有機電界発光素子 |
KR20160049083A (ko) * | 2014-10-24 | 2016-05-09 | (주)위델소재 | 퀴녹살린 유도체 화합물 및 이를 이용한 유기전계 발광소자 |
KR20160117823A (ko) * | 2015-03-31 | 2016-10-11 | (주)위델소재 | 퀴녹살린 유도체 화합물 및 이를 이용한 유기전계 발광소자 |
CN106047337A (zh) * | 2016-06-20 | 2016-10-26 | 武汉大学 | 一种含有喹喔啉单元的有机热致延迟荧光材料及其应用 |
CN107602582A (zh) * | 2016-12-12 | 2018-01-19 | 机光科技股份有限公司 | 有机化合物及使用该有机化合物的有机电致发光装置 |
CN107602538A (zh) * | 2017-09-29 | 2018-01-19 | 江苏三月光电科技有限公司 | 一种基于氮杂苯和喹喔琳的有机化合物及其在oled上的应用 |
CN110776500A (zh) * | 2019-11-29 | 2020-02-11 | 烟台显华化工科技有限公司 | 一类有机化合物及其应用 |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009170818A (ja) * | 2008-01-18 | 2009-07-30 | Mitsui Chemicals Inc | キノキサリン誘導体、およびそれを含む有機電界発光素子 |
KR20160049083A (ko) * | 2014-10-24 | 2016-05-09 | (주)위델소재 | 퀴녹살린 유도체 화합물 및 이를 이용한 유기전계 발광소자 |
KR20160117823A (ko) * | 2015-03-31 | 2016-10-11 | (주)위델소재 | 퀴녹살린 유도체 화합물 및 이를 이용한 유기전계 발광소자 |
CN106047337A (zh) * | 2016-06-20 | 2016-10-26 | 武汉大学 | 一种含有喹喔啉单元的有机热致延迟荧光材料及其应用 |
CN107602582A (zh) * | 2016-12-12 | 2018-01-19 | 机光科技股份有限公司 | 有机化合物及使用该有机化合物的有机电致发光装置 |
CN107602538A (zh) * | 2017-09-29 | 2018-01-19 | 江苏三月光电科技有限公司 | 一种基于氮杂苯和喹喔琳的有机化合物及其在oled上的应用 |
CN110776500A (zh) * | 2019-11-29 | 2020-02-11 | 烟台显华化工科技有限公司 | 一类有机化合物及其应用 |
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