CN113603688B - 一种n型有机界面材料及其制备方法与应用 - Google Patents
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/06—Peri-condensed systems
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6561—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing systems of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring or ring system, with or without other non-condensed hetero rings
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- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
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Abstract
本发明公开一种n型有机界面材料及其制备方法与应用,该材料以苝二酰亚胺为核心单元,氮位上连接柔性烷基链,含氢键及两亲性基团的烷基链作为侧链,得到两亲性n型有机界面材料。本发明以苝二酰亚胺为中心,在其湾位或肩位引入两亲性基团,得到基于苝酰亚胺的n型有机界面材料。该类材料在提高电子传输性能的同时还解决了电子传输层材料在极性溶剂中溶解性差的问题,可以作为电子传输层材料或界面修饰材料,广泛应用于高稳定性、高效率的有机光电器件。
Description
技术领域
本发明属于光电材料和应用技术领域,具体涉及一种n型有机界面材料及其制备方法与应用。
背景技术
高效的n型界面材料不仅可以大幅度提高有机光电器件的效率,还能保证器件长期稳定地工作。例如,在有机太阳能电池领域,n型界面材料起到了传输电子和阻挡空穴的双重作用,可以避免光生电子-空穴对在电池内部复合。近年来,有机光电功能材料发展非常迅速。对于实现有机太阳能电池器件性能的提高,其中一个关键因素就是获得高效平衡的载流子注入和传输。
研究发现在众多非富勒烯类材料中,苝二酰亚胺类衍生物在有机太阳能电池领域展现出良好的光电性能。该类材料合成简单,价格便宜,具有优良的光/化学稳定性,而且也具有优异的热稳定性和成膜性能,基于这类材料所制备的有机太阳能电池器件,呈现出高效的光电转换效率。最近我们构筑了一种含氢键的两亲性n型界面材料——脂肪族胺功能化苝二亚酰胺,它具有合适的偶极矩降低空气稳定金属Ag和Cu的功函数,n型界面材料侧链中的仲胺能与活性层中的光伏材料形成氢键,与活性层形成良好的接触。所得到的两亲性结构材料,既具有小分子结构确定的优点又具有聚合物优异的成膜性、可溶液加工的特性作为有机光电功能材料具有重要的应用价值。
发明内容
技术问题:
本发明的目的是提供一种n型有机界面材料及其制备方法与应用,可以采用溶液加工如旋涂、丝网印刷或喷墨打印的方法制备有机太阳能电池、有机电致发光器件、有机场效应晶体管的正置器件结构以及倒置器件结构中。通过优化器件结构和实施条件实现优异的光电特性,可以克服有机半导体材料电子传输能力不足、溶解性差等技术问题。
技术方案:
本发明提供一种n型有机界面材料,该材料以苝二酰亚胺n型结构骨架为核心单元,氮位上连接柔性烷基链,湾位或肩位上连接两亲性基团,该材料具有如下式Ⅰ所示结构:
其中,Ar1、Ar2、Ar3、Ar4、Ar5、Ar6、Ar7和Ar8为氢或两亲性基团;R是直链或支链烷基。
在一实施例中,所述两亲性基团为含胺基、仲胺基、季胺基、羧酸基、磺酸基、磷酸基官能团的结构单元。
在一实施例中,Ar1、Ar2、Ar3、Ar4、Ar5、Ar6、Ar7和Ar8各自独立的选择以下基团Am-1、Am-2、Am-3、Am-4、Am-5、Am-6、Am-7:
其中,R为直链或支链烷基。
在一实施例中,所述有机材料具有如下结构:
本申请还提供该两亲性苝二酰亚胺基n型有机界面材料的制备方法,具体按如下步骤进行:
将溴代苝二酰亚胺与含两亲性基团Ar1、Ar2、Ar3、Ar4、Ar5、Ar6、Ar7和Ar8的硼酸酯单体在催化剂条件下,进行偶联反应,制备得到n型有机界面材料;其反应过程如下式所示:
其中Ar为Ar1-Ar8中的一种或多种,但是Ar1-Ar8不能同时为氢。
在一实施例中,n型有机界面材料的制备方法,该制备方法具体包括以下步骤:
(1)将溴代苝二酰亚胺和含两亲性基团Ar1、Ar2、Ar3、Ar4、Ar5、Ar6、Ar7和Ar8的硼酸酯单体及相转移催化剂加入到反应瓶中。在惰性气体保护中加入催化剂,然后加入甲苯和碱性溶液,控温80-110℃条件下,避光反应12-48小时。
(2)反应结束后,用水淬灭反应,并冷却至室温,用二氯甲烷进行萃取、抽滤、柱层析、干燥后得到目标产物。
本发明同时提供了该类苝二酰亚胺基n型有机界面材料的应用方法,该类材料作为电子传输层材料或界面修饰层材料应用于有机电致发光器件、有机太阳能电池、电子纸、有机场效应晶体管、有机激光、储能器件、或传感器等领域。
有益效果:
本发明提供一种n型有机界面材料及其制备方法与应用,可以作为电子传输层材料或界面修饰层材料应用于有机电致发光器件、有机太阳能电池、电子纸、有机场效应晶体管、有机激光、储能器件、或传感器等。将两亲性基团引入到缺电子的苝二酰亚胺上,不仅提高了电子传输性能,同时还解决了在极性溶剂中溶解性差及成膜性差的技术难题。该材料具有优异的热稳定性、电子传输特性、溶解性、成膜性,是一类具有重要应用潜力的电子传输层材料。
附图说明
图1为本申请一实施例提供的n型有机界面材料XVII的质谱谱图。
图2为基于XVII的n型有机界面材料制备的有机太阳能电池的电流-电压密度曲线。
图3为对本申请一实施例提供的n型有机界面材料测量其外量子效率
具体实施方式
下面结合具体实施例对本发明做进一步说明。以下内容仅例示发明的原理。因此,虽未在本说明书中明确地进行说明或图示,但本领域技术人员可实现发明的原理而发明包括在发明的概念与范围内的各种装置。另外,应理解,本说明书中所列举的所有附有条件的术语及实施例在原则上仅明确地用于理解发明的概念,并不限制于像这样特别列举的实施例及状态。
本实施例提供的n型有机界面材料可以是如下的结构:
实施例1-1:
材料IX化合物的制备:
将1-溴-N,N'-双(十一烷基)苝-3,4,9,10-四羧酸二亚胺(1.15g,1.5mmol)与4-(3-(1-咪唑基)丙基氨基甲基)苯硼酸频哪醇酯(1.53g,4.5mmol)及TBAB(0.28g,0.86mmol)放入100mL的两口反应瓶中,抽换氮气三次,再向反应瓶中加入Pd(PPh3)4(0.5g,0.43mmol)并将其密封,再抽换氮气三次。向反应瓶中注入除氧的甲苯45mL及2mol/L的K2CO3溶液15mL,95℃反应24h。反应结束后,用水淬灭反应,并冷却至室温,用二氯甲烷进行萃取、抽滤、柱层析、干燥后得到目标产物材料IX(0.36g,产率为21.4%)。
实施例1-2:
材料XVII化合物的制备:
将1,7-二溴-N,N'-双(十一烷基)苝-3,4,9,10-四羧酸二亚胺(0.9g,1mmol)、4-(3-(1-咪唑基)丙基氨基甲基)苯硼酸频哪醇酯(1.3g,12mmol)、四丁基溴化胺(TBAB)(0.27g,0.8mmol)放入150mL的两口瓶中,将其用橡皮塞密封,抽换N2三次。然后迅速加入Pd(PPh3)4催化剂(0.49mg,0.43mmol),再抽换N2三次。最后,将鼓泡除氧后的甲苯(40mL)和2M的K2CO3水溶液(15mL)分别注入到反应瓶中,95℃下反应24h。反应结束后,用DCM溶剂和饱和NaCl溶液萃取3次,分离出的有机层经MgSO4干燥后抽滤并将溶液浓缩后得到的粗产物通过柱层析(洗脱剂PE:DCM=4:1)分离提纯,真空干燥箱烘干后得到纯净的产物XVII(1.18g,产率为42%)。
实施例1-3:
材料XXV化合物的制备:
将1,5,7-三溴-N,N'-双(十一烷基)苝-3,4,9,10-四羧酸二亚胺(0.47g,0.5mmol)与4-(3-(1-咪唑基)丙基氨基甲基)苯硼酸频哪醇酯(0.51g,1.5mmol)及TBAB(0.09g,0.28mmol)放入100mL的两口反应瓶中,抽换氮气三次,再向反应瓶中加入Pd(PPh3)4(0.5g,0.43mmol)并将其密封,再抽换氮气三次。向反应瓶中注入除氧的甲苯45mL及2mol/L的K2CO3溶液15mL,95℃反应24h。反应结束后,用水淬灭反应,并冷却至室温,用二氯甲烷进行萃取、抽滤、柱层析、干燥后得到目标产物材料XXV(0.45g,产率为33.4%)。
实施例1-4:
材料XXXXII化合物的制备:
将1,6,7,12-四溴-N,N'-双(十一烷基)苝-3,4,9,10-四羧酸二亚胺(0.20g,0.2mmol)与3-(4-(4,4,5,5-四甲基-1,3,2-二氧硼杂环-2-基)苯氧基)丙烷-1-磺酸钠(0.51g,1.2mmol)及TBAB(0.07g,0.22mmol)放入100mL的两口反应瓶中,抽换氮气三次,再向反应瓶中加入Pd(PPh3)4(0.25g,0.22mmol)并将其密封,再抽换氮气三次。向反应瓶中注入除氧的甲苯45mL及2mol/L的K2CO3溶液15mL,95℃反应24h。反应结束后,用水淬灭反应,并冷却至室温,用二氯甲烷进行萃取、抽滤、柱层析、干燥后得到目标产物材料XXXXII(0.09g,产率为21.7%)。
实施例1-5:
材料LV化合物的制备:
将1,5,6,7,12-五溴-N,N'-双(十一烷基)苝-3,4,9,10-四羧酸二亚胺(0.22g,0.2mmol)与N-丁基-N-乙基-4-(4,4,5,5-四甲基-1,3,2-二氧苯并呋喃-2-基)苯胺(0.45g,1.5mmol)及TBAB(0.07g,0.22mmol)放入100mL的两口反应瓶中,抽换氮气三次,再向反应瓶中加入Pd(PPh3)4(0.25g,0.22mmol)并将其密封,再抽换氮气三次。向反应瓶中注入除氧的甲苯45mL及2mol/L的K2CO3溶液15mL,95℃反应24h。反应结束后,用水淬灭反应,并冷却至室温,用二氯甲烷进行萃取、抽滤、柱层析、干燥后得到目标产物材料LV(0.074g,产率为23.4%)。
实施例1-6:
材料LXXII化合物的制备:
将1,2,5,6,8,11-六溴-N,N'-双(十一烷基)苝-3,4,9,10-四羧酸二亚胺(0.23g,0.2mmol)与((3-(4-(4,4,5,5-四甲基-1,3,2-二氧苯甲醛-2-基)苯基)丙基)氮杂炔基)二甲醇(0.57g,1.8mmol)及TBAB(0.07g,0.22mmol)放入100mL的两口反应瓶中,抽换氮气三次,再向反应瓶中加入Pd(PPh3)4(0.25g,0.22mmol)并将其密封,再抽换氮气三次。向反应瓶中注入除氧的甲苯45mL及2mol/L的K2CO3溶液15mL,95℃反应24h。反应结束后,用水淬灭反应,并冷却至室温,用二氯甲烷进行萃取、抽滤、柱层析、干燥后得到目标产物材料LXXII(0.14g,产率为37.4%)。
实施例1-7:
材料LXXIII化合物的制备:
将1,2,5,6,7,8,12-七溴-N,N'-双(十一烷基)苝-3,4,9,10-四羧酸二亚胺(0.25g,0.2mmol)与磷酸二乙酯(0.80g,2.1mmol)及TBAB(0.11g,0.34mmol)放入100mL的两口反应瓶中,抽换氮气三次,再向反应瓶中加入Pd(PPh3)4(0.5g,0.43mmol)并将其密封,再抽换氮气三次。向反应瓶中注入除氧的甲苯45mL及2mol/L的K2CO3溶液15mL,95℃反应24h。反应结束后,用水淬灭反应,并冷却至室温,用二氯甲烷进行萃取、抽滤、柱层析、干燥后得到目标产物材料LXXIII(0.21g,产率为41.4%)。
实施例1-8:
材料LXXV化合物的制备:
将1,2,5,6,7,8,11,12-八溴-N,N'-双(十一烷基)苝-3,4,9,10-四羧酸二亚胺(0.27g,0.2mmol)与磷酸二乙酯(0.92g,2.4mmol)及TBAB(0.11g,0.34mmol)放入100mL的两口反应瓶中,抽换氮气三次,再向反应瓶中加入Pd(PPh3)4(0.5g,0.43mmol)并将其密封,再抽换氮气三次。向反应瓶中注入除氧的甲苯45mL及2mol/L的K2CO3溶液15mL,95℃反应24h。反应结束后,用水淬灭反应,并冷却至室温,用二氯甲烷进行萃取、抽滤、柱层析、干燥后得到目标产物材料LXXV(0.17g,产率为31.4%)。
实施例2-1:
有机太阳能电池器件的制备:
有机太阳能电池器件制备过程:器件结构为ITO(氧化铟锡)/PEDOT:PSS(聚3,4-乙撑二氧噻吩:聚苯乙烯磺酸盐)/PBDB-T-2F:IT-4F(聚[(2,6-(4,8-双(5-(2-乙基己基-3-氟)噻吩-2-基)-苯并[1,2-b:4,5-b']二噻吩])-alt-(5,5-(1',3'-二-2-噻吩-5',7'-双(2-乙基己基)苯并[1',2'-c:4',5'-c']二噻吩-4,8-二酮)]:3,9-二(2-亚甲基-((3-(1,1-二氰亚甲基)-5,6-二氟)-吲哚酮))-5,5,11,11-四(4-己基苯基)-二硫杂环[2,3-d:2',3'-d']-s-吲哚杂环[1,2-b:5,6-b']二硫杂环/n型有机界面/Ag。器件的具体制备方法如下:将ITO基底通过紫外、臭氧处理清洁15min,然后按丙酮、洗涤剂、去离子水、异丙酮的顺序续超声清洗20min。通过旋涂法将PEDOT:PSS(4083)溶液以3000r/min的速度旋涂到处理后的ITO基板上,在空气中150℃退火10min,之后转入到充满氮气的手套箱;活性层PBDB-T-2F:IT-4F(给受体按1:1的比例共混,用氯苯溶解,总浓度为10mg/mL)在手套箱中以2400r/min的转速旋涂在PEDOT:PSS(4083)上,然后在100℃下退火处理10min;n型有机界面材料(浓度为0.5mg/mL溶于甲醇)以3000r/min的转速旋涂在活性层上;最后转入蒸镀箱抽真空,当舱内压强小于1×10-5bar时开始蒸镀,Ag的厚度为100nm,基于n型有机界面材料XVII所制备的有机太阳能电池器件的电流-电压密度曲线如图2所示,根据图示结果,可充分说明本申请制备的器件具有高效稳定的光电转换性能。
实施例2-2~2-8:
有机太阳能电池器件的测试:
除了使用表1中记载的各化合物来代替化合物IX作为电子传输材料,按照与实施例2-1相同的方法来制备有机太阳能电池器件。对于所得的有机太阳能电池器件,按照与实施例2-1相同的方法,测定其短路电流(Jsc),开路电压(Voc),填充因子(FF),光电转换效率(PCE)结果如表1所示,光电转换效率均在6%以上,说明将此类n型有机界面材料作为电子传输层应用于有机太阳能电池中具有良好的电子传输特性。
表1:
实施例3-1:
有机发光二极管器件的制备:
有机发光二极管器件的制备过程:器件结构为ITO/IX/Alq3(8-羟基喹啉铝)/NPB((N-N’-二苯基-N-N’-(1-萘基)-1,1’-联苯-4,4’-二胺)/Al。将ITO基底通过紫外、臭氧处理清洁15min,然后按丙酮、洗涤剂、去离子水、异丙酮的顺序依次超声清洗20min。通过旋涂法将电子传输层IX溶液以3000r/min的速度旋涂到处理后的ITO基板上,在空气中150℃退火10min,之后转入到充满氮气的手套箱;发光层Alq3在手套箱中以2400r/min的转速旋涂在IX上,然后在100℃下退火处理10min;空穴传输层NPB以3000r/min的转速旋涂在发光层上;最后转入蒸镀箱抽真空,当舱内压强小于1×10-5bar时开始蒸镀,Al的厚度为100nm。
实施例3-2~3-8:
有机发光二极管器件的制备:
除了使用表2中记载的各化合物来代替化合物IX作为电子传输层,按照与实施例3-1相同的方法来制备有机发光二极管器件。对于所得的有机发光二极管器件,按照与实施例3-1相同的方法,测定其启亮电压(V),荧光亮度(cd/m2),结果如表2所示,荧光亮度均超过3000cd/m2,充分说明将此类n型有机界面材料作为电子传输层应用于有机发光二极管器件中具有良好的电子传输特性。
表2:
实施例4
为对本申请实施例1-2提供的n型有机界面材料测量其外量子效率
通测量实施例1-2制备的n型有机界面材料XVII的外量子效率,测试结果参见图3,其中积分面积对应器件的短路电流。由图3可知,本申请制备的n型有机界面材料短路电流性能极佳。
上述实施例仅例示性说明本发明的原理及其功效,而非用于限制本发明。任何熟悉此技术的人士皆可在不违背本发明的精神及范畴下,对上述实施例进行修饰或改变。因此,举凡所属技术领域中具有通常知识者在未脱离本发明所揭示的精神与技术思想下所完成的一切等效修饰或改变,仍应由本发明的权利要求所涵盖。
Claims (6)
4.如权利要求1所述的n型有机界面材料的制备方法,其特征在于,该制备方法包括以下步骤:
(1)将溴代苝二酰亚胺和含两亲性基团Ar1、Ar2、Ar3、Ar4、Ar5、Ar6、Ar7和Ar8原料及相转移催化剂加入到反应瓶中在惰性气体保护中加入催化剂然后加入甲苯和碱性溶液,控温80-110℃条件下,避光反应12-48小时;
(2)反应结束后,用水淬灭反应,并冷却至室温,用二氯甲烷进行萃取、抽滤、柱层析、干燥后得到目标产物。
5.如权利要求3所述的n型有机界面材料的制备方法,其特征在于,反应步骤(1)中,溴代苝二酰亚胺和含两亲性基团Ar1、Ar2、Ar3、Ar4、Ar5、Ar6、Ar7和Ar8的摩尔比在1:2到1:5之间。
6.一种如权利要求1所述的n型有机界面材料的应用,其特征在于,该材料作为电子传输层或界面修饰层应用于有机电致发光器件、有机太阳能电池、电子纸、有机场效应晶体管、有机激光、储能器件、或传感器中。
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