CN114891026B - 一类基于吡喃环的A-D-π-A型小分子受体材料及其应用 - Google Patents
一类基于吡喃环的A-D-π-A型小分子受体材料及其应用 Download PDFInfo
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Abstract
本发明属于有机光伏太阳能电池领域,具体涉及一类基于吡喃环的A‑D‑π‑A型小分子受体材料及其应用。以吡喃环为强电子给体(D)单元,噻吩或二噻吩环戊二烯为π桥,氰基茚酮衍生物为强电子受体(A)末端单元,吡喃环的引入可有效地增加材料的溶解性、拓宽了吸收、保证活性层具有良好的相分离,有利于提升太阳能电池的短路电流。将聚合物给体材料(PBDB‑T)与此类小分子受体材料共混作为活性层,应用于溶液加工型聚合物太阳能电池,能量转换效率达到了14.37%。本发明实现了基于吡喃环桥联的小分子受体材料在聚合物太阳能电池中的高效能量转换。
Description
技术领域
本发明属于有机光伏太阳能电池领域,具体涉及一类基于吡喃环的A-D-π-A型小分子受体材料及其应用。
背景技术
近年来,随着人类社会赖以生存的化石能源面临枯竭,环境污染日益严重,高耗能低能效的能源利用已经无法满足未来经济发展的需要。建立高效资源利用、降低能耗、保护生态环境和有效控制温室气体,开发出清洁、可持续发展的新能源显得尤为迫切。而有机太阳能电池(Organic Solar Cells,OSCs)由于具有材料来源广、质量轻、成本低、可溶液加工、柔性半透明、可大面积制造等优点,是继硅基太阳能电池之后,近二十年来太阳能开发利用的一个重要研究方向。
在本体异质结有机太阳能电池中,性能优异的光活性层是获得高效率有机太阳能电池的关键材料,它主要由给体材料和受体材料组成。经过几十年的研究,给体材料和富勒烯电子受体材料获得了迅速发展,大量性能优异的小分子、聚合物给体材料和一些富勒烯衍生物受体材料被开发出来;新兴的非富勒烯受体材料近年也得到了快速发展,形成了小分子和聚合物两大类非富勒烯受体材料。
2015年,占肖卫教授课题组开创性提出A-D-A型“梯形稠环电子受体”新理念,开发出了窄带隙和高电子迁移率非富勒烯电子受体ITIC,并与宽带隙给体聚合物PTB7-TH共混,获得了PCE为6.8%的非富勒烯有机太阳能电池(NF-OSCs)。但这些基于刚性稠环梯形核SMAs的分子结构相对复杂,往往需要通过化学键的联稠合,合成步骤繁杂、纯化难度大、成本高等关键问题严重制约了其规模化合成和大规模器件制备。
发明内容
基于吡喃环的A-D-π-A型小分子受体材料研究相对较少,吡喃环具有强给电子能力和宽的吸收光谱,A-D-π-A的结构具有非对称性,有利于解决分子堆积和取向的精确调节、减弱分子强聚集效应和强结晶性带来的相分离过大以及电荷传输不平衡等问题。因此,开发结构简单的、基于吡喃环的A-D-π-A型小分子受体材料,具有重大意义。
本发明旨在提供一类全新的、结构简单的小分子受体材料。基于吡喃环的A-D-π-A型小分子受体材料合成路线简单、产率高、成本低、稳定性好;吡喃环的引入,能有效地增加材料溶解性、拓宽吸收、保证活性层具有良好的相分离,提高聚合物太阳能电池的短路电流的作用。π桥具有扩展分子的共轭平面,有利于拓宽吸收光谱、降低禁带宽度,有效地调控分子的光谱与能级的作用。整个A-D-π-A型的不对称结构的分子具有较高偶极矩差和介电常数,有利于分子面向面取向,降低激子束缚能,提升激子解离和电荷传输,从而使分子的载流子迁移率提升。
为了实现上述技术目的,本发明提供的一类基于吡喃环的A-D-π-A型小分子受体材料,具有式1所示的分子结构:
其中,式1中的X为H,F,Cl原子中的一种;
Y为O,S,Se原子中的一种;
R1独立地选自直连C8~C20烷基或可取代的芳烷基中的一种;
Ar为下列式2中基团的一种;
式2中,R独立地选自C8~C24烷基中一种;
Z独立地选自H,F,Cl,OR,SR,可取代的芳烷基,可取代的芳硫烷基基团中一种。
π为下列式3中基团的一种:
式3中,R2独立地选自C8~C24烷基中一种;
Z独立地选自H,F,Cl,OR,SR,可取代的芳烷基,可取代的芳硫烷基基团中一种;W独立地选自C,Si,Ge原子中一种。
基于吡喃环的A-D-π-A型小分子受体材料优选结构式如下:
本发明提供的小分子受体材料具有以下特点:
(1)其吸收光谱红移,吸收边超过900nm;
(2)与A-D-A’-D-A型对称小分子受体相比,主要优势在于减少了单元之间的C-C单键,有利于在薄膜中形成J-聚集;
(3)不对称的A-D-π-A结构在能级匹配方面有一定优势,更容易达到开路电压和短路电流的平衡;
(4)此类小分子受体同时具有合成简单化和结构多样化的特点。
本发明的应用在于:将该类基于吡喃环的A-D-π-A型小分子做为受体材料,与能级相匹配的聚合物给体材料PBDB-T共混作为活性层,在溶液加工条件下制备太阳能电池器件,实现太阳能器件的高效光电转换。
PBDB-T的分子结构如下式所示:
聚合物太阳能电池光活性层中,小分子受体材料与PBDB-T共混质量比为1:1;活性层的厚度介于20nm-300nm之间。
溶液加工包括旋涂、刷涂、喷涂、浸涂、辊涂、印刷或喷墨打印;其中,所用溶剂为有机溶剂。
所述的有机太阳电池器件包括氧化锡铟(ITO)导电玻璃阳极、阳极修饰层、光活性层、阴极修饰层、阴极,器件结构为ITO/PEDOT:PSS(40nm)/PBDB-T:LYY2(D:A=1:1)/PDIN(5nm)/Al(100nm)。
附图说明:
图1为本发明SMA1三氯甲烷溶液的紫外-可见吸收光谱和固体薄膜的紫外-可见吸收光谱;
图2为本发明SMA2三氯甲烷溶液的紫外-可见吸收光谱和固体薄膜的紫外-可见吸收光谱;
图3为本发明SMA1固体薄膜的循环伏安曲线;
图4为本发明SMA2固体薄膜的循环伏安曲线;
图5为本发明SMA1和SMA2的太阳能电池器件的J-V曲线;
图6为本发明SMA1和SMA2的太阳能电池器件的EQE曲线。
具体实施方式
下面通过具体实施例对本发明作进一步说明,但这些具体实施方案不以任何方式限制本发明的保护范围。
实施例1
基于吡喃环的A-D-π-A型小分子受体材料的合成。
SMA1和SMA2的合成路线如下:
1.1化合物1的合成
在200mL单口瓶中加入2,5-二溴对苯二甲酸二甲酯(4.7g,13.4mmol)、三丁基(3-甲氧基噻吩-2-基)锡烷(19.0g,47.1mmol)、Pd(PPh3)Cl2(280.0mg,0.4mmol)和100mL甲苯,氮气保护下在110℃下反应过夜。将反应液中甲苯旋除,DCM萃取,旋转蒸馏去除溶剂,粗产品以PE:DCM(3:1,v:v)为洗脱剂进行柱层析,得黄色固体为化合物1(4.2g,产率75.1%)。1HNMR(400MHz,CDCl3)δ7.82(s,2H),7.26(d,J=5.2Hz,2H),6.87(d,J=5.2Hz,2H),3.78(s,12H)。
1.2化合物2的合成
在50ml单口瓶中加入化合物1(4g,9.6mmol)和30mL DCM,在冰水浴中缓慢滴加BBr3(24g,9.2mL),在常温下反应6h。将反应液缓慢倒入水中,抽滤,用饱和NaHCO3溶液和水洗涤,得黄绿色固体为化合物2(2.94g,产率94.2%)。1H NMR(400MHz,DMSO)δ7.62(d,J=4.0Hz,2H),7.56-7.34(m,4H)。
1.3化合物3的合成
在100mL双口瓶中加入化合物2(1g,3.1mmol)和10mL无水THF,氮气保护下在冰水浴下缓慢滴加新制备的正十二烷格氏试剂(40mL),在70℃下反应过夜。将反应冷却后旋转蒸馏除去溶剂,DCM萃取(加入HCl调节pH=1~2),旋转蒸馏去除溶剂。在50mL单口瓶中加入未经进一步处理的粗产物、30mL甲苯和对甲苯磺酸(58.3mg,0.3mmol),在130℃下回流反应过夜。将反应冷却后旋转蒸馏除去溶剂,DCM萃取,旋转蒸馏去除溶剂,粗产品以PE为洗脱剂进行柱层析,得淡黄色固体为化合物3(1.37g,产率46.1%)。1H NMR(500MHz,CDCl3)δ7.04(d,J=5.3Hz,2H),6.77(s,2H),6.68(d,J=5.3Hz,2H),1.99-1.93(m,4H),1.89-1.82(m,4H),1.37(ddd,J=17.4,12.1,7.3Hz,8H),1.24(d,J=19.4Hz,72H),0.88(s,3H),0.87(s,6H),0.86(s,3H).
1.4化合物4的合成
将50mL双口瓶抽真空换氮气,置于冰水浴中预冷5min,加入5mL 1,2-二氯乙烷,再预冷5min,加入三氯氧磷(394.5mg,2.6mmol),再缓慢滴加DMF(37.6mg,0.5mmol),在冰水浴中反应1h,然后升温至室温反应1h,将溶于20mL 1,2-二氯乙烷的化合物3(500.0mg,0.5mmol)缓慢滴加到反应中,升温至70℃回流反应过夜。反应结束后冷却至室温,将反应液滴加到饱和K2CO3溶液中搅拌至无气泡产生,DCM萃取,干燥,旋转蒸馏去除溶剂,粗产品以PE:DCM(3:1,v:v)为洗脱剂进行柱层析,得橙色油状液体为化合物4(403.2mg,产率78.4%)。1H NMR(500MHz,CDCl3)δ9.79(s,1H),7.29(s,1H),7.11(d,J=5.3Hz,1H),6.91(s,1H),6.79(s,1H),6.69(d,J=5.3Hz,1H),1.94(dd,J=11.5,4.2Hz,4H),1.89(dd,J=10.9,4.4Hz,4H),1.38(s,4H),1.29-1.20(m,76H),0.87(dd,J=7.0,6.6Hz,12H).
1.5化合物5的合成
在50mL单口瓶中加入化合物4(250.0mg,0.25mmol)、6-溴-4,4-双(2-乙基己基)-4H-环戊[2,1-b:3,4-b']二噻吩-2-甲醛(133.8mg,0.26mmol)、碳酸铯(244.5mg,0.75mmol)、三甲基乙酸(25.5mg,0.25mmol)、Pd2(dba)3(11.4mg,0.01mmol)、TOMPP(50.3mg,0.09mmol)和25mL甲苯,氮气保护在110℃下反应6h。反应结束后冷却至室温,旋转蒸馏去除溶剂,DCM萃取,干燥,旋转蒸馏去除溶剂,粗产品以PE:DCM(2:1,v:v)为洗脱剂进行柱层析,得红色油状液体为化合物5(221.6mg,产率62.0%)。1H NMR(300MHz,CDCl3)δ9.84(s,1H),9.80(s,1H),7.56(t,J=2.5Hz,1H),7.30(s,1H),7.11(s,1H),6.91(s,1H),6.83(s,1H),6.75(s,1H),1.96-1.90(m,8H),1.43-1.34(m,6H),1.24(d,J=8.4Hz,80H),1.02-0.92(m,14H),0.87(d,J=6.3Hz,10H),0.84(s,2H),0.76(t,J=6.6Hz,6H),0.63(d,J=5.2Hz,6H).
1.6SMA1的合成
在50mL单口瓶中加入化合物5(100mg,0.07mmol)、5,6-二氯-3-(二氰基亚甲基)茚-1-酮(73.7mg,0.28mmol)和25mL三氯甲烷,加入0.1mL吡啶,在75℃下回流反应6h。反应结束后冷却至室温,旋转蒸馏去除溶剂,DCM萃取,干燥,旋转蒸馏去除溶剂,粗产品以PE:DCM(2:1,v:v)为洗脱剂进行柱层析,得黑色固体粉末为SMA1(101.0mg,产率77.9%)。1HNMR(400MHz,CDCl3)δ8.92(s,1H),8.78(s,1H),8.77(s,1H),8.75(s,1H),7.95(s,1H),7.92(s,1H),7.64(s,1H),7.48(s,1H),7.18(s,1H),7.12(s,1H),6.94(s,1H),6.79(s,1H),1.99-1.93(m,8H),1.41(d,J=7.0Hz,6H),1.22(s,80H),1.02-0.93(m,14H),0.87-0.85(m,10H),0.83(d,J=0.8Hz,2H),0.76(dd,J=6.5,2.9Hz,6H),0.67(d,J=7.1Hz,3H),0.63(d,J=7.3Hz,3H).
1.7SMA2的合成
在50mL单口瓶中加入化合物5(100mg,0.07mmol)、5,6-二氟-3-(二氰基亚甲基)茚-1-酮(64.4mg,0.28mmol)和25mL三氯甲烷,加入0.1mL吡啶,在75℃下回流反应6h。反应结束后冷却至室温,旋转蒸馏去除溶剂,DCM萃取,干燥,旋转蒸馏去除溶剂,粗产品以PE:DCM(2:1,v:v)为洗脱剂进行柱层析,得黑色固体粉末为SMA2(110.8mg,产率85.5%)。1HNMR(500MHz,CDCl3)δ8.89(s,1H),8.76(s,1H),8.53(dd,J=15.7,9.2Hz,2H),7.71–7.61(m,3H),7.48(s,1H),7.17(s,1H),7.11(s,1H),6.94(t,J=2.0Hz,1H),6.79(s,1H),2.04–1.93(m,12H),1.44–1.38(m,4H),1.26–1.21(m,71H),1.04–0.92(m,17H),0.87–0.83(m,14H),0.76(dd,J=11.6,6.8Hz,7H),0.65(dt,J=15.1,4.7Hz,7H).
实施例2
一类基于吡喃环的A-D-π-A型小分子受体材料的光物理性能表征测试。基于新型受体单元D-A型聚合物材料的紫外-可见吸收光谱通过HP-8453紫外-可见光谱仪测定SMA1和SMA2的光物理性能。
图1,2分别为有机小分子受体材料SMA1,SMA2在氯仿溶液和薄膜状态下的紫外-可见吸收光谱。由图1,2可知,它们在氯仿溶液中具有很强的吸收(ε=1.6-2.0×105),其固体膜的吸收峰在600-1100nm范围内,可归属于分子内的电荷转移(ICT)作用。薄膜相对于溶液的吸收约有50nm的红移。同时可测得小分子受体材料的光学带隙分别为1.36eV(SMA1)和1.36eV(SMA2)(公式为Eg=1240/λ,其中Eg为光学带隙,λ为薄膜起始吸收)。
实施例3
一类基于吡喃环的A-D-π-A型小分子受体材料的电化学性能表征测试。循环伏安曲线采用CHI630E电化学分析仪测试,在乙腈溶液中以0.1M六氟磷酸四丁铵(Bu4NPF6)作为支持电解质。
小分子受体SMA1,SMA2在固体膜中的循环伏安曲线如图3,4所示。由计算公式EHOMO=-(Eox-E1/2,Fc/Fc++4.80)eV,得出它们的HOMO能级分别为-5.53eV,-5.53eV。由计算公式ELUMO=-(Ered-E1/2,Fc/Fc++4.80)eV,得出它们的LUMO能级为-3.94eV,-3.90eV。于是计算得出SMA1,SMA2的电化学带隙为1.59eV,1.63eV。
实施例4
一类基于吡喃环的A-D-π-A型小分子受体材料的太阳能电池器件性能表征测试。基于该类型小分子受体材料的有机太阳能电池器件包括:氧化锡铟(ITO)导电玻璃阳极、阳极修饰层、光活性层、阴极,器件结构为ITO/PEDOT:PSS(40nm)/PBDB-T:LYY2(D:A=1:1)/PDIN(5nm)/Al(100nm)。
受体小分子SMA1,SMA2与给体聚合物PBDB-T在共混的情况下,它们的光伏器件的J-V曲线如图5所示。当掺杂比例为1:1和热退火处理1min时,基于PBDB-T:SMA1器件的开路电压为0.83V,短路电流为23.51mA/cm2,填充因子为73.63%,光电转换效率为14.37%。基于PBDB-T:SMA2器件的开路电压为0.84V,短路电流为22.88mA/cm2,填充因子为62.49%,光电转换效率为12.07%。
受体小分子SMA1,SMA2与给体聚合物PBDB-T在共混的情况下,光伏器件的EQE的关系如图6所示,其EQE响应范围都为300-1000nm,在430-870nm范围内都超过了60%,而SMA1在660nm处为最大EQE值,达76.8%,SMA2在658nm处为最大EQE值,达73%。
尽管结合了优选实施例对本发明进行了说明,但本发明并不局限于上述实施例,应当理解所附权利要求概括了本发明的范围。在本发明构思的指导下,本领域的技术人员应当意识到,对本发明各实施例方案所进行的一定的改变,都将被本发明的权利要求书的精神和范围所覆盖。
Claims (5)
1.一类基于吡喃环的A-D-π-A型小分子受体材料,其特征在于,所述受体材料结构式如下:
;
所述受体材料与聚合物给体材料PBDB-T共混形成聚合物太阳能电池的光活性层。
2.根据权利要求1所述小分子受体材料,其特征在于,所述聚合物太阳能电池光活性层中,小分子受体材料与PBDB-T共混质量比为1:1。
3.根据权利要求1所述小分子受体材料,其特征在于,所述活性层的厚度介于20 nm-300 nm之间。
4.根据权利要求1所述小分子受体材料,其特征在于,所述的活性层通过溶液加工法实现。
5.根据权利要求4所述小分子受体材料,其特征在于,所述溶液加工包括旋涂、刷涂、喷涂、浸涂、辊涂、印刷或喷墨打印;其中,溶液所用溶剂为有机溶剂。
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