CN102762630A - 具有高载流子迁移率的绿色可溶性共轭聚合物 - Google Patents
具有高载流子迁移率的绿色可溶性共轭聚合物 Download PDFInfo
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- CN102762630A CN102762630A CN2010800234451A CN201080023445A CN102762630A CN 102762630 A CN102762630 A CN 102762630A CN 2010800234451 A CN2010800234451 A CN 2010800234451A CN 201080023445 A CN201080023445 A CN 201080023445A CN 102762630 A CN102762630 A CN 102762630A
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- polymkeric substance
- dioxy
- thiophene
- furans
- tellurium
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Abstract
一种具有高电荷转移迁移率的供体-受体(DA)π-共轭聚合物,所述聚合物具有多个D1kAD1k部分,其中k是1或2,D1是一种具有至少一个增溶侧链的供体单元,A是一种受体单元,并且所述供体-受体(DA)π-共轭聚合物具有多个位于D1xAD1x部分之间的D2m间隔序列,其中m是1到6,且D2是另一种供体单元,所述另一种供体单元的所有原子在至少一种该单元能呈现的构象中是共平面的。所述DAπ-共轭聚合物能反射蓝绿色,深绿色,或黄绿色。所述DAπ-共轭聚合物的空间电荷限制(SCL)零场空穴迁移率为至少1x 10-6cm2V-1s-1。
Description
相关申请的交叉引用
本申请要求2009年5月26日提交的第US61/181,058号美国临时申请优先权,该申请的整体以引入方式并入本发明,包括所有图表、表格或者图示。
政府支持
本发明是在美国空军科学研究局(AFOSR)的一项合同编号为UF Project 59866的研究项目支持下完成的。美国政府对本发明享有一定的权利。
背景技术
分子系统中引发的能带混合涉及富电子和贫电子π-共轭取代基,属于一种“供体-受体”(DA)方法,已经应用于下列物质的设计和合成:发光半导体、用于有机薄膜晶体管的n-沟道和二级半导体、用于化学生物传感器的有机活性组分和非放射性有机电致变色材料。DA的另外一个重要应用涉及在电磁波谱的可见和/或近红外(NIR)区域具有吸收的低能隙光伏材料,尤其是用于本体-异质结太阳能电池能使太阳能转换得到改进。供体-受体π-共轭聚合物在创新的高性能柔性集光技术中的使用备受关注。这些DAπ-共轭聚合物允许通过结构控制进行简单带隙工程以及力学变形以获得柔性电子系统。此外,DAπ-共轭聚合物在低成本、高产量的集光设备的制造中具有潜在的应用前景。DAπ-共轭聚合物溶液在例如用于汽车或屋顶的大面积太阳能电池或由精细印刷的光敏阵列制作的便携电子设备的应用中相对于使用无机等价物的方法具有相当大的优势。
尽管供体-受体理论首次由Havinga等人报道用于大分子系统[Havinga等人,Synth.Met.1993,55,299],但是其在最近才由合成的传导聚合物证实在光电池效率方面具有优良的表现。已经证实,在系统中的效率可高达约5%,但是用于实用系统的规范相当少。总之,使用DAπ-共轭聚合物获得的低能量转换效率可归因于:1)它们的吸收光谱通常限于可见光谱的一小部分(典型地在红光区域);和2)当用于固状设备时,它们本身的载流子迁移率低。
反射绿色的双波段吸收材料在可见光区域显示两个吸光率极值,具有480-560nm范围的透射窗口(window of transmission)。尽管对光电聚合物有约20年的热点研究,但是双波段吸收绿色光电聚合物鲜有报道,主要是因为形成共轭聚合物材料的重复单元的分子结构设计的复杂性。在获得双波段吸收绿色光电聚合物的同时实现所要求的光学性质和所希望的载流子迁移率尚未见报道。目前为止,对于这些聚合物材料,已报道的载流子迁移率较低,这限制了在固态设备中的电荷传输,不能用于制备切实可行的太阳能转换设备。
目前文献描述的中性态是绿色的π-共轭聚合物,双波段吸收材料,具有令人失望的载流子迁移率,转而未能促进它们应用于集光设备。这些聚合物的载流子迁移率令人失望归因于:1)缺少有利的分子间相互作用,主要是少π-堆积;2)不利的大的链间距(或层间距);和3)相对较少延伸的共轭,归因于聚合物主链低水平的可平面性。有效的本体-异质结太阳能电池要求高载流子迁移率,以致光生激子(成双的电子-空穴对)能够经受在设备活性层内的扩散和分离过程,随后将分离的电荷迅速传输至收集电极。除非太阳能电池材料显示充分高的载流子迁移率,否则分离的电荷在收集前重新结合,设备显示较弱的太阳能转换。因此,开发一种具有高载流子迁移率且易于加工的绿色π-共轭聚合物对于集光应用是值得期待的。
发明内容
本发明的实施方式涉及具有高载流子迁移率的供体-受体(DA)π-共轭聚合物,所述聚合物的空间电荷限制(SCL)零场空穴迁移率为至少1x 10-6cm2V-1s-1。DAπ-共轭聚合物是多个D1kAD1k部分,其中k为1或2,D1是一种或更多种含有至少一个增溶侧链的供体单元,且A是一种受体单元,所述的多个D1kAD1k部分被D2m间隔序列分隔,其中m为1到16且D2是另一种供体单元。所述的D2单元具有如下结构:所述单元的所有原子位于一个单一平面上,以致所述间隔序列呈现的构象能产生延伸的共轭且允许DA聚合物之间进行有利的堆积,这提高了DAπ-共轭聚合物的载流子迁移率。DAπ-共轭聚合物能够被设计成在两个波段吸收光,且反射蓝绿色、深绿色或黄绿色。
DAπ-共轭聚合物的D1单元可以是3,4-二氧噻吩,3,4-二氧吡咯,3,4-二氧呋喃,3,4-二氧硒吩,或3,4-二氧碲吩,3,4-烷撑二氧噻吩(3,4-alkylenedioxythiophene),3,4-烷撑二氧吡咯(3,4-alkylenedioxypyrrole),3,4-烷撑二氧呋喃(3,4-alkylenedioxyfuran),3,4-烷撑二氧硒吩(3,4-alkylenedioxyselenophene),或3,4-烷撑二氧碲吩(3,4-alkylenedioxytelurophene),所述的D1单元含有侧链并且当k是2时,所述的D1单元可以是稠合的芳香杂环。D1上的增溶侧链可以是支链或直链C3-C30烷基、或烯烃基(alkylene)或烷基芳基,并且可以是未被中断的、未被取代的、被中断的或被一个或更多个官能团取代,所述的官能团例如羟基、氨基、醚基,酯基、羰基、羧酸氰基或卤基。
DAπ-共轭聚合物的A单元是一个含氮电子接受杂环。这种杂环的例子包括苯并噻二唑、噻二唑并喹喔啉、喹喔啉、噻吩并噻二唑、噻吩并吡嗪、吡嗪并喹喔啉、苯并双噻二唑和噻二唑并噻吩吡嗪,所述的杂环可以被取代或未被取代。
DAπ-共轭聚合物的D2单元独立为芳香族和杂芳香族单元,所述D2单元的结构固定在一个平面构象中或呈现一个平面构象,因为这些单元中的原子的共平面性能促进所希望的高载流子迁移率。能够使用的杂芳香族单元包括噻吩、吡咯、呋喃、硒吩和碲吩单元,所述的噻吩、吡咯、呋喃、硒吩和碲吩单元可以未被取代或在3和4位被下列基团取代:羟基、苯氧基、乙烯氧基、甲酰氧基、氰基、氨基、卤基(氟,氯,溴或碘)、羧酸、桥连1,2-亚乙烯基二氧基、桥连1,2-亚苯基二氧基,或所述的杂芳香族单元可以是以杂芳香族环为基础形成的任意平面多环芳香族单元。
本发明的另一种实施方式是DAπ-共轭聚合物与一种受体混合。能够与DAπ-共轭聚合物混合的合适的受体包括巴克敏斯特富勒烯(buckminsterfullerene)类分子和无机金属氧化物,所述的巴克敏斯特富勒烯类分子包括PCBM类,例如[6,6]-苯基-C61-丁酸甲酯(PC60BM)、[6,6]-苯基-C71-丁酸甲酯(PC70BM)和其他取代的C60或C70巴克敏斯特富勒烯。
附图说明
图1是根据本发明一种实施方式所述的二氧噻吩-苯并噻二唑(DOT-BTD)供体-受体聚合物的特征图,所述聚合物允许调制吸收光谱,且具有良好的电荷传输性质,其中X表示P1的重复单元中不存在间隔序列。
图2显示根据本发明一种实施方式所述的控制组聚合物和DA-共聚物,其中聚合物a)P1,b)P2和c)P3,在甲苯溶液和薄膜中的光学吸收光谱,其光谱在最大吸收处被校正。
图3是根据本发明一种实施方式所述的制备单体的一种反应方案,M1是制备聚合物P1的单体或构成最后DAπ-共轭聚合物的重复单元的单体的一部分,所述重复单元为聚合物P1、P2和P3提供了带隙调制和可加工性。
图4是根据本发明实施方式所述的将单体M1转化为单体M2和M3以及使它们聚合形成DAπ-共轭聚合物P1,P2,和P3的方案。
图5显示根据本发明的一种实施方式所述的用于制备具有高载流子迁移率的绿色可溶性共轭聚合物的可供选择的聚合方案。
图6显示根据本发明一种实施方式所述的基于异质结(BHJ)的太阳能电池的I-V曲线,设备结构为:ITO/PEDOT/PX:PC60BM/LiF/Al,且PX=P1,P2或P3,并采用最佳的聚合物∶PCBM组成,其中暗电流曲线是由P1制成的设备获得,其它曲线都对应于AM 1.5太阳照度,100mW cm-2(蓝色,绿色和红色)。插入的照片显示的是当从背后照亮时(使得Al接触点显示黑色)的P3制成的聚合物∶PCBM的比率为1∶8的设备。
具体实施方式
本发明的实施方式涉及一种供体-受体(DA)π-共轭聚合物的制备,所述DAπ-共轭聚合物用于一种固态设备(例如太阳能电池或其它集光设备)时,具有大载流子迁移率。在本发明的一种实施方式中,所述DAπ-共轭聚合物为双波段吸收聚合物,它们的中性态显示(反射)蓝绿色、深绿色或黄绿色。所述DAπ-共轭聚合物的空间电荷限制(SCL)零场空穴迁移率为至少1x 10-6cm2V-1s-1。所述DAπ-共轭聚合物包括一个重复单元,所述重复单元具有一个能提供带隙粗调的结构部分,所述结构部分赋予了一种绿色色调,并使得所述聚合物易于加工,包括溶解加工。所述新的DAπ-共轭聚合物还包含一个间隔序列,所述间隔序列能够促进序列中相邻芳香环形成一个共平面构象,所述共平面构象能使共轭长度延伸、形成π-堆积和有利的层间距,使得在环境条件下可能获得大载流子迁移率。所述间隔片段的单元的组成使得单元中所有原子位于一个单一平面上。所述DAπ-共轭聚合物的重复单元部分见图1所示。
如图1所示,所述重复单元的一部分在一个DAD序列中显示三个芳香族杂环,其中一个贫电子受体单元位于2到4个富电子供体单元之间以提供双波段吸收(主要为红和蓝光),结果产生绿色并且可以通过改变单元的结构以调制色调。这部分的供体单元被足够大和柔性的取代基取代,所述取代基与杂环耦合以使得合成聚合物具有可溶性和可熔性。所述的足够大的取代基为包含这些单元的DAπ-共轭聚合物提供了良好的加工特性,包括从溶液或者从熔体加工聚合物薄膜和其它形式的能力。尽管所述供体单元具有同样的结构通常便于重复单元中所述部分的制备,但是本发明的一些实施方式中该部分的供体单元是不同的。
如图1所示,新的DAπ-共轭聚合物的重复单元中,各个DAD序列被另一部分(即由两个或更多个芳香族单元组成的一个间隔片段)所分隔。在本发明的一些实施方式中,所述间隔片段中非芳香族共轭基团可位于芳香环之间。所述重复单元的另一部分提供的结构允许对DAD序列的带隙进行微调但被合并成一体,以促进多个DAπ-共轭聚合物之间的平面性和π-堆积,从而导致所述DA聚合物具有高载流子迁移率。所述间隔片段部分中的芳香族单元的芳香环上没有取代基,所述的取代基会迫使所述单元结构中的一些原子位于所述芳香环规定的平面之外。尽管图1中以噻吩显示,但所述的芳香族或共轭单元可以是各种结构,并且所述的多个芳香族或共轭单元的结构可以相同或不同。
如图2所示,DAπ-共轭聚合物在电磁波谱可见光区域内的两个波段上显示光吸收。这些吸收允许透射窗口在490-580nm范围,所述透射窗口允许由这些DA聚合物反射得到绿色。图2中可以看出,聚合物P1在大约450到500nm波长范围没有显著吸收,所述DA聚合物显示蓝色。包含一个合适的间隔片段的聚合物在450到500nm范围具有显著吸收,显示绿色色调。一个所希望的间隔片段是能与所述重复单元另一部分的富电子供体单元一起提供显著程度的芳香族单元的共平面性。这种平面性有助所合成聚合物在设备中的电荷传输性质。
通过控制DAπ-共轭聚合物重复单元的结构,在可见光谱区内设定一个合适的吸收带的同时可对能隙进行微调。新的DAπ-共轭聚合物重复单元的DAD部分的变形能产生中性态绿色和一种所希望的色调,所述变形可按照Beaujuge等2008年10月29日提交的名为“Greento Transmissive Soluble Electrochromic Polymers”的国际申请PCT/US2008/081599中公开的方法实施,,此处以引用方式将该国际申请并入本发明。本发明所述的DAπ-共轭聚合物的间隔片段提供了多个供体单元,所述供体单元固定在一种构象中或能呈现一种构象,所述构象中单元中的所有原子都位于一个单一平面上。通过包含平面供体单元,促进了共轭延伸及链-链接触,从而使DAπ-共轭聚合物获得相当优越的载流子迁移率,其空间电荷限制(SCL)零场空穴迁移率为至少1x 10-6cm2V-1s-1。这些可溶解和熔融加工的DAπ-共轭聚合物在可见光谱区显示双波段吸收,具有在480-550nm范围的透射窗口,结果产生绿色。由于包含新的间隔片段,DAπ-共轭聚合物P3能有效收集太阳光并具有高载流子迁移率。
图3是一种DAD序列的制备方案,所述DAD序列可作为单体进一步用于制备新型DAπ-共轭聚合物,如图4所示。
如图3所示,通过使用一种已知化学转换,能够形成一个3,4-取代二氧噻吩中间体3。这个供体前体可被单官能团化,例如,通过锂化随后通过与三甲基氯化锡缩合形成富电子中间体4。所述的单官能团化3,4-取代二氧噻吩三甲基锡烷4能与贫电子溴代2,1,3-苯并噻二唑5在钯介导的交叉耦合反应中对称地耦合,产生M1。所述的供体-受体砌块M1具有四个平面内的增溶侧链,所述的增溶侧链规定了最终的DAπ-共轭聚合物的溶剂加工性能。如图4所示,所述的砌块M1可使用一种温和的氧化试剂(例如氯化铁)进行聚合以得到一种DAπ-共轭聚合物P1,P1作为一种没有间隔序列的控制组聚合物,用以说明本发明含有间隔序列的DAπ-聚合物的优越性。所述的砌块M1能够被溴化形成一种中间体M1’,随后该中间体M1’可用具有小的增溶基团(3,4-二甲氧基噻吩中的甲氧基)的各种杂环化合物对称地官能团化以生成M2或用未取代的噻吩对称地官能团化以生成M3。这些低氧化电势的低聚体M2和M3能在一种温和的氧化试剂(如氯化铁)存在下进行聚合生成缺少平面D2单元的聚合物P2和具有本发明实施方式所述的平面单元并具有宽广的吸收的聚合物P3。下述表1给出了用上述公开方式合成的典型聚合物的分子量、光学特性和热稳定性。
表1 凝胶渗透色谱法(GPC)估算的共聚物P1,P2,和P3(来自四氢呋喃)的分子量和它们本身的最大吸收(溶液和固态)
a肩宽.b氮气下通过热重分析仪(TGA)测量的初始分解温度
图5显示根据本发明实施方式制备DAπ-共轭聚合物的两种方案。第一种方案等同于图4所示的本发明实施方式所述的制备两种特定聚合物的方案。图5中,D2供体单元组成的间隔序列是平面单元且最终位于所述重复单元(序列)的第一部分D1kAD1k之间,其中k=1或2。D2单元可以相同或者不同,如此使得在给出的D1kAD1k的任意一侧的D2单元可以相同或不同,D2序列中的任意一个D2单元可以相同或者不同,且能够以对称的、不对称的或随机的方式分布在D1kAD1k部分周围。任意给出的D2单元可以是单一芳香环单元或稠合芳香环单元。它们的功能是通过增大芳香族单元的共平面来提高聚合物的有效共轭长度,并允许聚合物链之间进行有利的接触、置换和相互反应。可作为D2被应用的杂环单元包括噻吩,吡咯,呋喃,硒吩,碲吩,3,4-二羟基噻吩,3,4-二羟基吡咯,3,4-二羟基呋喃,3,4-二羟基硒吩,3,4-二羟基碲吩,3,4-二苯氧基噻吩,3,4-二苯氧基吡咯,3,4-二苯氧基呋喃,3,4-二苯氧基硒吩,3,4-二苯氧基碲吩,3,4-二乙烯氧基噻吩,3,4-二乙烯氧基吡咯,3,4-二乙烯氧基呋喃,3,4-二乙烯氧基硒吩,3,4-二乙烯氧基碲吩,3,4-二甲酰氧基噻吩,3,4-二甲酰氧基吡咯,3,4-二甲酰氧基呋喃,3,4-二甲酰氧基硒吩,3,4-二甲酰氧基碲吩,3,4-(1,2-亚乙烯基)二氧噻吩,3,4-(1,2-亚乙烯基)二氧吡咯,3,4-(1,2-亚乙烯基)二氧呋喃,3,4-(1,2-亚乙烯基)二氧硒吩,3,4-(1,2-亚乙烯基)二氧碲吩,3,4-(1,2-亚苯基)二氧噻吩,3,4-(1,2-亚苯基)二氧吡咯,3,4-(1,2-亚苯基)二氧呋喃,3,4-(1,2-亚苯基)二氧硒吩,3,4-(1,2-亚苯基)二氧碲吩,3,4-二氰基噻吩,3,4-二氰基吡咯,3,4-二氰基呋喃,3,4-二氰基硒吩,3,4-二氰基碲吩,3,4-二氨基噻吩,3,4-二氨基吡咯,3,4-二氨基呋喃,3,4-二氨基硒吩,3,4-二氨基碲吩,3,4-二卤代噻吩,3,4-二卤代吡咯,3,4-二卤代呋喃,3,4-二卤代硒吩,3,4-二卤代碲吩,噻吩-3,4-二羧酸,吡咯-3,4-二羧酸,呋喃-3,4-二羧酸,硒吩-3,4-二羧酸,碲吩-3,4-二羧酸,3,4-二卤代噻吩,3,4-二卤代吡咯,3,4-二卤代呋喃,3,4-二卤代硒吩,3,4-二卤代碲吩,以及其它平面芳香族和杂芳香族单元。
D1kAD1k部分的D1单元是包含侧链的富电子供体D1单元,所述侧链有适当的大小和结构以允许在溶液或熔体中加工。所述的D1单元可以是被一个侧链取代的3,4-二氧噻吩、3,4-二氧吡咯、3,4-二氧呋喃、3,4-二氧硒吩、或3,4-二氧碲吩、3,4-烷撑二氧噻吩、3,4-烷撑二氧吡咯、3,4-烷撑二氧呋喃、3,4-烷撑二氧呋喃、3,4-烷撑二氧硒吩或3,4-烷撑二氧碲吩,所述的侧链取代是在3和/或4-氧基取代基处、在烷撑桥上或在吡咯的氮上,所述侧链具有有充足大小和结构的基团以使得最终的DAπ-共轭聚合物可溶解于一种或更多种溶剂中。所述的侧链可以是支链或者直链的C3到C30烷基,或烯烃基或烷基芳香基。所述侧链可以被中断或被一种或更多种官能团取代以增强在选择溶剂中的溶解性,所述官能团例如羟基、氨基、醚基、酯基、羰基、羧酸氰基和卤基。多个D1单元可以相同或者不同,当不同时D1单元可以在A单元周围以一种对称、不对称或随机的方式分布。当k=2时,一对杂环可以通过一种共同的取代基稠合,如一个共同的取代基都与两个杂环的3位连接。所述的共同的取代基可以是桥连在两个环之间的碳、氧、氮、硫或硅。所述的稠合环具有一个或多个增溶侧链,所述增溶侧链与一个桥连碳、硅或氮连接或与所述环的任意位置连接。
所述受体单元A可以是任意缺电子单元,且可以是一个稠合或非稠合芳香环单元。例如所述A单元可以是未被取代或取代的苯并噻二唑,噻二唑并喹喔啉,喹喔啉,噻吩并噻二唑,噻吩并吡嗪,吡嗪并喹喔啉,苯并二噻二唑,或噻二唑并噻吩吡嗪。
在图5的第一种方案中,m=1到3的D2单元的序列通过交叉缩合反应与D1kAD1k序列的两端连接,形成一个D2mD1kAD1kD2m序列。D2m单元可以被单分散(所有m序列是相等的)或多分散(存在各种m序列)。D2mD1kAD1kD2m是一种聚合单体,通过自缩合反应生成DAπ-共轭聚合物(D2mD1kAD1kD2m)n。在第二种方案中,m=1到6的D2单元的序列与D1kAD1k序列聚合,其中D2m是D1kAD1k的补充单体,用于交叉缩合生成所希望的DAπ-共轭聚合物(D1kAD1kD2m)n,所述m=1到6的D2单元的序列可以相同或不同,可以是对称的、不对称的或随机的,且可以是单分散或多分散的。
上述具体实施方式包含烷氧基以增强在有机溶剂中的溶解性和加工性,所述有机溶剂如氯仿、四氢呋喃、甲苯、氯苯和二氯苯。在本发明的其他实施方式中,更多极性或离子型侧链可与DAD序列的供体分子连接,以使聚合物在更宽的范围内具有溶解性,某些情况下是可溶于更多极性溶剂中。这些可供选择的侧链包括低聚醚、酯基、酰胺、羧酸、磺酸盐、胺和其他极性官能团。极性和离子型侧链的一种优势是可用于与一种基底的特殊相互反应,在一种设备形成中,所述DAπ-共轭聚合物沉积在所述基底上。例如,所述极性或离子型侧链能够促进DAπ-共轭聚合物吸附到氧化物表面以制备二氧化钛基太阳能电池(Graetzel Cells)。在本发明的一种实施方式中,侧链可以是一种酯基,所述酯基可采用Reynolds等人于2007年8月2日公开的名为“Chemical Defunctionalization of Polymeric Alkylenedioxyheterocyclics”的国际专利申请WO2007/087587教导的方式转换成醇、羧酸或羧酸衍生物,所述国际申请此处以引用方式并入本发明。
图6显示DAπ-共轭聚合物的载流子性能增强,本发明一种实施方式所述的DAπ-共轭聚合物P3含有一个由两个未取代的噻吩单元组成的间隔序列,并且由P3制成的光伏太阳能电池的电流密度在一个较宽的外加偏压范围内是由控制组P1甚至是P2制成的电池的两倍,所述控制组P1不含间隔,所述P2的结构中具有相对较小的取代基,不能使得所有的原子都位于噻吩环规定的平面内。所述的电池结构为ITO/PEDOT/PX:PC60BM/LiF/Al,其中ITO是一种透明的铟-锡-氧化物电极,PEDOT是一个聚(3,4-乙撑二氧噻吩)内层,PX是一种DAπ-共轭聚合物,包括一个取代的巴克敏斯特富勒烯PC60BM([6,6]-苯基-C61-丁酸甲酯),LiF位于铝电极上。用P3制成的电池不仅如图6所示表现出最高的光伏性能,而且P3具有最高的热稳定性,在氮气氛围中高达320℃,该特征与所述DA聚合物的结构具有良好的π-堆积是一致的。在光伏设备的制备中,所述DA聚合物能够通过各种方式很容易地沉积,如旋转涂布、喷雾沉积(spray-casting)、喷墨印刷或冲压。
本发明的一种实施方式中,具有高电荷迁移率的DAπ-共轭聚合物与PCBM类(如PC60BM或PC70BM)或其它类似的官能团化巴克敏斯特富勒烯混合以进一步增强光电性能,使其超过未混合的DAπ-共轭聚合物。在这些混合物中,DA聚合物是作为电子供体,PCBMs是作为电子受体。令人意外的,发现这些混合物在最佳组成下的空穴电流显著高于在未混合的DAπ-共轭聚合物中观测的电流。在混合物的DA聚合物相的空穴迁移率相对于所述的DA聚合物提高了一个数量级或者更多,如下面给出的表2所示。即使所述混合物中的DA聚合物相被显著地稀释(这种情况下,由于渗透不完全,会导致电荷传输性能下降),还是发生了空穴迁移的增加。以混合物的重量计,PCBMs的重量含量多达95%。所述的DAπ-共轭聚合物可与其它受体混合,包括无机金属氧化物,例如氧化锌。
表2 聚合物和它们的优选混合物的零场空穴迁移率,其中迁移率是将J-V数据代入无陷阱的单载子空间电荷限制电流(SCLC)模型得到
DAπ-共轭聚合物 | 零场空穴迁移率(cm2V-1s-1) |
P1 | 5.4x 10-8 |
P2 | 6.9x 10-7 |
P3 | 3.9x 10-6 |
P1:PC60BM | 2x 10-6 |
P2:PC60BM | 5x 10-6 |
P3:PC60BM | 1x 10-5 |
溶液可加工的、中性态为绿色的、具有增强的电荷传输性能的共轭聚合物可制成光伏设备,例如图6的插入照片显示的设备。这些元件可以是美观的且可用作,例如,发电显示器、集光窗口、或军事上的伪装发电设备以及其他应用。溶液可加工的共轭聚合物相比于传统的无机相对物(例如多晶硅),有可能显著地降低成本,易于扩展,质量更轻并表现出优越的机械性能,例如柔性和耐用性。
除柔性光电元件应用外,本发明实施方式所述的高效材料DAπ-共轭聚合物的一种应用是作为多晶硅太阳能电池的替换物,从而降低成本。从紫外区域(大约400nm)、大部分可见光区域直至近红外区域(约800-900nm)的波长范围吸收太阳光的能力是希望拥有的,以优化太阳能电池的效率。这些新的共轭聚合物在太阳能电池中,能够同时作为光吸收体和对于一种受体(例如巴克敏斯特富勒烯衍生物PCBM)的电子供体。有利地,对于一个特定的DAπ-共轭聚合物的HOMO和LUMO能级绝对值的调制能力允许所述聚合物的结构处于所希望的光激发态,以促进电子转移到一个特定的受体。在电子转移后,产生的空穴和电子载体被有效收集,这是因为DAπ-共轭聚合物的间隔序列使得聚合物具有高度平面性并在聚合物的主链之间发生链间强相互作用,从而导致高电荷迁移率。
此处涉及或引用的所有专利,专利申请,临时申请和出版物的整体通过引文方式并入本发明,包括所有图表和表格,在这样的范围内,它们与本说明书的明确教导是不相矛盾的。
需要理解的是,此处描述的实施例和实施方式仅用于说明的目的,本领域普通技术人员可以据此作出各种变形或改变,这些变形和改变都包含在本申请的精神和范围之内。
Claims (15)
1.一种具有高载流子迁移率的供体-受体(DA)π-共轭聚合物,包含:
多个D1kAD1k部分,其中k为1或2,D1独立包含一种供体单元,所述供体单元含有至少一个增溶侧链,A包含一种受体单元;和
多个D2m间隔序列,其位于所述D1xAD1x部分之间,其中m为1到6,D2独立包含另一种供体单元,所述的另一种供体单元具有如下结构:所述另一种供体单元的所有原子在至少一种构象中是共平面的,其中所述DAπ-共轭聚合物的空间电荷限制(SCL)零场空穴迁移率为至少1x 10-6cm2V-1s-1。
2.如权利要求1所述的DAπ-共轭聚合物,其中所述DAπ-共轭聚合物反射蓝绿色,深绿色,或黄绿色。
3.如权利要求1所述的DAπ-共轭聚合物,其中所述D1包含3,4-二氧噻吩,3,4-二氧吡咯,3,4-二氧呋喃,3,4-二氧硒吩,或3,4-二氧碲吩,3,4-烷撑二氧噻吩,3,4-烷撑二氧吡咯,3,4-烷撑二氧呋喃,3,4-烷撑二氧硒吩,或3,4-烷撑二氧碲吩,其中所述增溶侧链与所述D1的氧基或任意碳连接。
4.如权利要求1所述的DAπ-共轭聚合物,其中所述D1k包含D12,所述D12具有一对杂环,所述一对杂环通过两者之间的一个共同的取代基稠合,所述共同的取代基包含一个碳、氧、氮、硫或硅桥,其中所述增溶侧链与所述D12的任意一个碳、氧、氮、硫或硅连接。
5.如权利要求4所述的DAπ-共轭聚合物,其中所述D1k包含D12,所述的D12是稠合的二噻吩并环戊二烯或稠合的二噻吩并噻咯的稠合衍生物,其中所述增溶侧链与所述D12的任意一个碳、氧、氮、硫或硅连接。
6.如权利要求1所述的DAπ-共轭聚合物,其中所述侧链包含支链或直链C3到C30烷基、或烯烃基、或烷基芳基,所述侧链是未被中断的、未被取代的、被中断的或被一种或更多种官能团取代,所述官能团包括羟基、氨基、乙醚基、酯基、羰基、羧酸氰基或卤基。
7.如权利要求1所述的DAπ-共轭聚合物,其中所述A包含一个含氮电子接受杂环。
8.如权利要求7所述的DAπ-共轭聚合物,其中所述含氮电子接受杂环包含苯并噻二唑,噻二唑并喹喔啉,喹喔啉,噻吩并噻二唑,噻吩并吡嗪,吡嗪并喹喔啉,苯并双噻二唑或噻二唑并噻吩吡嗪,并且所述含氮电子接受杂环被取代或未被取代。
9.如权利要求1所述的DAπ-共轭聚合物,其中所述D2包含一个芳香族和杂芳香族单元。
10.如权利要求9所述的DAπ-共轭聚合物,其中所述杂芳香族单元包含噻吩,吡咯,呋喃,硒吩,碲吩,3,4-二羟基噻吩,3,4-二羟基吡咯,3,4-二羟基呋喃,3,4-二羟基硒吩,3,4-二羟基碲吩,3,4-二苯氧基噻吩,3,4-二苯氧基吡咯,3,4-二苯氧基呋喃,3,4-二苯氧基硒吩,3,4-二苯氧基碲吩,3,4-二乙烯氧基噻吩,3,4-二乙烯氧基吡咯,3,4-二乙烯氧基呋喃,3,4-二乙烯氧基硒吩,3,4-二乙烯氧基碲吩,3,4-二甲酰氧基噻吩,3,4-二甲酰氧基吡咯,3,4-二甲酰氧基呋喃,3,4-二甲酰氧基硒吩,3,4-二甲酰氧基碲吩,3,4-(1,2-亚乙烯基)二氧噻吩,3,4-(1,2-亚乙烯基)二氧吡咯,3,4-(1,2-亚乙烯基)二氧呋喃,3,4-(1,2-亚乙烯基)二氧硒吩,3,4-(1,2-亚乙烯基)二氧碲吩,3,4-(1,2-亚苯基)二氧噻吩,3,4-(1,2-亚苯基)二氧吡咯,3,4-(1,2-亚苯基)二氧呋喃,3,4-(1,2-亚苯基)二氧硒吩,3,4-(1,2-亚苯基)二氧碲吩,3,4-二氰基噻吩,3,4-二氰基吡咯,3,4-二氰基呋喃,3,4-二氰基硒吩,3,4-二氰基碲吩,3,4-二氨基噻吩,3,4-二氨基吡咯,3,4-二氨基呋喃,3,4-二氨基硒吩,3,4-二氨基碲吩,3,4-二卤代噻吩,3,4-二卤代吡咯,3,4-二卤代呋喃,3,4-二卤代硒吩,3,4-二卤代碲吩,噻吩-3,4-二羧酸,呋喃-3,4-二羧酸,硒吩-3,4-二羧酸,碲吩-3,4-二羧酸,3,4-二卤代噻吩,3,4-二卤代吡咯,3,4-二卤代呋喃,3,4-二卤代硒吩,或3,4-二卤代碲吩。
11.如权利要求1所述的DAπ-共轭聚合物,其中所述A包含苯并噻二唑,D1包含含有C3到C30烷基的二氧噻吩且D2包含噻吩。
12.如权利要求1所述的DAπ-共轭聚合物,进一步包含一种PCBM形成一种混合物。
13.如权利要求12所述的DAπ-共轭聚合物,其中所述PCBM为[6,6]-苯基-C61-丁酸甲酯(PC60BM),[6,6]-苯基-C71-丁酸甲酯(PC70BM),或一个相当的官能团取代的巴克敏斯特富勒烯。
14.如权利要求12所述的DAπ-共轭聚合物,其中所述PCBM以所述混合物重量计多达95%。
15.如权利要求1所述的DAπ-共轭聚合物,进一步包含一种无机金属氧化物形成一种混合物。
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CN105199083A (zh) * | 2015-09-11 | 2015-12-30 | 中国石油大学(华东) | 一种聚合物太阳能电池光活性层用长波吸收共聚物给体材料及其制备方法 |
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IT1401129B1 (it) * | 2010-07-16 | 2013-07-12 | Eni Spa | Processo per la sintesi di composti benzotiadiazolici |
CA2805638A1 (en) | 2010-08-02 | 2012-02-09 | University Of Florida Research Foundation, Inc. | Processing method for water soluble polymeric materials |
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