CN102164926B - 用于光电器件的活性材料 - Google Patents
用于光电器件的活性材料 Download PDFInfo
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- CN102164926B CN102164926B CN200980138171.8A CN200980138171A CN102164926B CN 102164926 B CN102164926 B CN 102164926B CN 200980138171 A CN200980138171 A CN 200980138171A CN 102164926 B CN102164926 B CN 102164926B
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- Prior art keywords
- bis
- thiophene
- benzo
- dodecyloxy
- electrode
- Prior art date
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- 239000011149 active material Substances 0.000 title claims description 7
- 229920000547 conjugated polymer Polymers 0.000 claims abstract description 24
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 12
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims description 21
- 229920000642 polymer Polymers 0.000 claims description 18
- 238000000576 coating method Methods 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 7
- 239000002861 polymer material Substances 0.000 claims description 5
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims description 4
- UUIQMZJEGPQKFD-UHFFFAOYSA-N Methyl butyrate Chemical compound CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 claims description 3
- 239000002674 ointment Substances 0.000 claims 2
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 claims 1
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 abstract description 7
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 abstract description 5
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- 125000005677 ethinylene group Chemical group [*:2]C#C[*:1] 0.000 abstract description 3
- 125000003107 substituted aryl group Chemical group 0.000 abstract description 2
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- 239000000126 substance Substances 0.000 description 41
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- 0 C[C@](*)c1c(C)c2n[s]nc2c(C)c1N Chemical compound C[C@](*)c1c(C)c2n[s]nc2c(C)c1N 0.000 description 20
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- 125000005605 benzo group Chemical group 0.000 description 5
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- 238000010586 diagram Methods 0.000 description 5
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Abstract
一种具有重复单元的共轭聚合物,所述重复单元具有式(I)的结构,其中A1、A2、R1和R2独立地选自质子、含至多18个碳原子的烷基、含至多18个碳原子的烷氧基、氰基、硝基、芳基和取代的芳基,且其中Ar选自亚乙烯基、亚乙炔基、单环亚芳基、双环亚芳基、多环亚芳基、单环杂亚芳基、双环杂亚芳基、多环杂亚芳基,和稠合或连接的1至5个这样的基团。
Description
技术领域
本发明的实施方案涉及用于光电器件的活性材料和使用该材料的光电器件;更具体而言涉及作为用于光电器件的活性层材料的共轭聚合物。
相关技术讨论
本文引用的所有参考文献(包括论文、公开的专利申请和专利)的内容以引用方式并入本文。
基于有机材料(小分子和聚合物)的电子器件已引起广泛的关注。这类器件包括有机发光器件(OLED)(Tang,C.W.;VanSlyke,S.A.;Appl.Phys.Lett.1987,51,913)、有机光伏电池(OPV)(Tang,C.W.Appl.Phys.Lett.1986,48,183)、晶体管(Bao,Z.;Lovinger,A.J.;Dodabalapur,A.Appl.Phys.Lett.1996,69,3066)、双稳态器件和存储器件(Ma,L.P.;Liu,J.;Yang,Y.Appl.Phys.Lett.2002,80,2997)等。聚合物电子设备的最突出的一些属性在于,它们可以是极低成本的、灵活的、以低能耗运行,可使用高通量加工法制得,并可具有多种应用(Forrest,S.R.Nature 2004,428,911)。为了满足低成本的要求,溶液法是高度合意的。
太阳能电池,也称为光伏(PV)电池或器件,由入射光产生电功率。术语“光”在本文广义地使用,其是指可包括可见光、紫外光和红外光的电磁辐射。通常,由多种无机半导体构建PV电池,所述无机半导体为例如晶体硅、多晶硅和非晶硅、砷化镓、碲化镉和其他材料。最近,已使用有机材料来构建PV电池。
太阳能电池的特征在于,它们可以将入射太阳能转化为可用的电功率的效率。采用晶体硅或非晶硅的器件在商业应用中占有优势,一些已获得23%或更高的效率。然而,由于在没有显著的效率降低缺陷的大晶体制备中所固有的问题,有效的晶体基器件,特别是表面积大的晶体基器件的制备困难且昂贵。在另一方面,高效非晶硅器件仍然受到稳定性问题的困扰。现有的市售非晶硅电池具有4至8%的稳定效率。最近的努力集中于使用有机光伏电池以获得可接受的光伏转化效率以及经济的制造成本和其他可能的有利性质。
当将PV器件连接在负载上并用光辐照时,其产生光生电压。当PV器件在无任何外部电子负载下进行辐照时,PV器件产生其可能的最大电压,V开路,或VOC。若PV器件在其电接触短路下进行辐照,则产生最大短路电流,或ISC。(电流通常称为“I”或“J”。)当实际用于产生功率时,PV器件连接至有限的电阻负载,其中输出功率以电流和电压的乘积,I×V给出。由PV器件产生的最大总功率固有地不能超过乘积ISC×VOC。当优化负载值以获得最大功率提取时,电流和电压分别具有值I最大和V最大。太阳能电池的品质因数为填充因子,ff(或FF),其定义为:
其中ff总是小于1,因为在实际使用中永远不会同时获得ISC和VOC。尽管如此,当ff接近1时,器件更有效。
当适当能量的电磁辐射入射到半导体有机材料,例如,有机分子晶体(OMC)材料或聚合物上时,光子可被吸收而产生激发分子态。该能量吸收与电子由最高占据分子轨道(HOMO)中的束缚态跃迁至最低非占据分子轨道(LUMO),或者等同地,空穴从LUMO跃迁至HOMO相关。在有机薄膜光电导体中,认为产生的激发态为激子,即束缚态的电子-空穴对,其作为准粒子而进行传递。在复合之前,激子可具有可估计的寿命。为了产生光电流,电子-空穴对必须分开,例如在两种不同的接触的有机薄膜之间的给体-受体界面处分开。这两种材料的界面称为光伏异质结。若电荷不分开,则它们或者通过发射具有比入射光的能量更低的光而辐射地彼此复合(称为淬灭),或者通过产生热而非辐射地彼此复合。这两种结果在PV器件中均是不希望的。在传统的半导体理论中,用于形成PV异质结的材料通常表示为p(给体)型或n(受体)型。文中,n型表示大多数载流子类型为电子。这可以视为材料具有许多处于相对自由的能量状态的电子。p型表示大多数载流子类型为空穴。这样的材料具有许多处于相对自由的能量状态的空穴。本底大多数载流子浓度的类型主要取决于缺陷或杂质的无意而为的掺杂。杂质的类型和浓度决定了在最高占据分子轨道(HOMO)和最低非占据分子轨道(LUMO)之间的间隙(称为HOMO-LUMO间隙)内的费米能量或费米能级的值。费米能量表征由占据几率等于1/2的能量值表示的分子量子能量状态的统计占据。接近LUMO能量的费米能量表示电子为主要载流子。接近HOMO能量的费米能量表示空穴为主要载流子。因此,费米能量为传统半导体的主要特征性质,且PV异质结通常为p-n界面。
有机半导体中的显著性质为载流子迁移率。迁移率测量电荷载流子能够响应电场移动通过导电材料的容易度。与自由载流子浓度相反,载流子迁移率大部分由有机材料的本征性质如晶体对称性和周期性决定。适当的对称性和周期性可产生HOMO能级的更高的量子波函数重叠从而产生更高的空穴迁移率,或者类似地,产生LUMO能级的更高重叠,从而产生更高的电子迁移率。此外,有机半导体的给体或受体性质可能与更高的载流子迁移率不一致。结果是,由给体/受体标准预测器件构造可能不会被实际器件性能所证实。由于有机材料的这些电子性质,常常使用术语“空穴传输层”(HTL)或“电子传输层”(ETL)而不是将它们定名为“p型”或“给体型”和“n型”或“受体型”。在该指定方案中,ETL优先为电子传导的,且HTL优先为空穴传输的。
相比于传统硅基器件,有机PV电池具有许多潜在优点。有机PV电池是轻质的,所用的材料经济,并可沉积在低成本衬底如柔性塑料箔上。然而,有机PV器件通常具有相对较低的量子产率(所吸收的光子与所产生的载流子对之比,或电磁辐射与电转化效率之比),大约为1%或更小。认为这部分地由于本征光导过程的二阶性质。即,载流子产生需要激子产生、扩散和电离。然而,激子的扩散长度(LD)通常比光吸收长度小得多,需要在使用具有多个或高度折叠的表面的厚的并因此电阻性的电池或者使用具有低的光吸收效率的薄的电池之间权衡。
共轭聚合物为含有沿主链的π-电子共轭单元的聚合物。它们可用作用于一些类型的光电器件如聚合物发光器件、聚合物太阳能电池、聚合物场效应晶体管等的活性层材料。作为聚合物太阳能电池材料,共轭聚合物应具有一些性质,如高迁移率、良好的太阳光捕集、良好的加工性和适当的分子能级。已证实一些共轭聚合物为良好的太阳能电池材料。例如,聚(对苯撑乙烯)的一些衍生物如MEH-PPV和MDMO-PPV,聚(3-烷基噻吩)的一些衍生物如P3HT和P3OT,和一些具有杂环芳香环的共轭聚合物如聚[2,6-(4,4-双-(2-乙基己基)-4H-环戊[2,1-b;3,4-b′]-二噻吩)-交替(alt)-4,7-(2,1,3-苯并噻二唑)](PCPDTBT)已成功用作光活性层材料。尽管基于这些聚合物的太阳能电池器件的能量转化效率达到了至多4-5%,但是这比无机半导体太阳能电池的能量转化效率要低得多。因此,本领域相应地需要具有改进的光电效应的共轭聚合物。
发明内容
根据本发明的一个实施方案的共轭聚合物具有重复单元,该重复单元具有式(I)的结构:
其中A1、A2、R1和R2独立地选自氢、具有至多18个碳原子的烷基、含至多18个碳原子的烷氧基、氰基、硝基、芳基和取代的芳基,并且
其中Ar可以是亚乙烯基;亚乙炔基;单环、双环或多环亚芳基;单环、双环或多环杂亚芳基,其中杂原子可在一个或多个环中;或者可以是稠合或连接的1至5个这样的前述基团。
根据本发明的一个实施方案的电子器件或光电器件包含根据本发明的一个实施方案的共轭聚合物材料。
根据本发明的一个实施方案的电子器件或光电器件具有第一电极、与所述第一电极间隔开的第二电极,和在第一电极和第二电极之间设置的活性材料层。所述活性层包含根据本发明的一个实施方案的共轭聚合物。
附图说明
通过参照附图阅读如下详细描述可更好地理解本发明,其中:
图1为根据本发明的一个实施方案的光电器件的示意图;
图2为根据本发明的另一实施方案的光电器件的示意图;
图3显示了如下聚合物的吸收光谱:聚[4,8-二(十二烷氧基)-苯并[1,2-b;3,4-b]二噻吩-2,6-二基]-共-[2,3-二苯基喹喔啉-5,8-二基](具有实心方形的线)、聚[-2,6-(4,8-二(十二烷氧基)-苯并[1,2-b;3,4-b]二噻吩)](具有空心圆形的线),和聚[4,8-二(十二烷氧基)-苯并[1,2-b;3,4-b]二噻吩-2,6-二基]-共-[2,1,3-苯并噻二唑-4,7-二基](具有空心三角形的线);
图4显示了如下聚合物的吸收光谱:聚[4,8-二(十二烷氧基)-苯并[1,2-b;3,4-b]二噻吩-2,6-二基]-共-[噻吩并[3,4-b]吡嗪-5,7-二基](具有实心方形的线)、聚[4,8-二(十二烷氧基)-苯并[1,2-b;3,4-b]二噻吩-2,6-二基]-共-[3,4-乙撑二氧基噻吩-2,5-二基](具有空心圆形的线),和聚[4,8-二(十二烷氧基)-苯并[1,2-b;3,4-b]二噻吩-2,6-二基]-共-[(E)-1,2-亚乙烯基](具有空心三角形的线);
图5显示了如下聚合物的吸收光谱:聚[4,8-二(十二烷氧基)-苯并[1,2-b;-4.7-b]二噻吩-2,6-二基]-共-[噻吩-2,5-二基](具有实心方形的线)、聚[4,8-二(十二烷氧基)-苯并[1,2-b;3,4-b]二噻吩-2,6-二基]-共-[苯并[c][1,2,5]硒二唑-4,7-二基](具有空心圆形的线),和聚[4,8-二(十二烷氧基)-苯并[1,2-b;3,4-b]二噻吩-2,6-二基]-共-[5,5′-(2,2′-(4,7-苯并[c][1,2,5]噻二唑-二基)-双(3-己基噻吩)-二基](具有空心三角形的线);
图6显示了在铂电极上的聚合物膜在0.1mol/L Bu4NPF6,CH3CN溶液中的循环伏安图:聚[4,8-二(十二烷氧基)-苯并[1,2-b;3,4-b]二噻吩-2,6-二基]-共-[2,3-二苯基喹喔啉-5,8-二基](具有实心方形的线)、聚[-2,6-(4,8-二(十二烷氧基)-苯并[1,2-b;3,4-b]二噻吩)](具有空心圆形的线)、聚[4,8-二(十二烷氧基)-苯并[1,2-b;3,4-b]二噻吩-2,6-二基]-共-[2,1,3-苯并噻二唑-4,7-二基](具有空心三角形的线),以及聚[4,8-二(十二烷氧基)-苯并[1,2-b;3,4-b]二噻吩-2,6-二基]-共-[噻吩并[3,4-b]吡嗪-5,7-二基](具有实心三角形的线);
图7显示了在铂电极上的聚合物膜在0.1mol/L Bu4NPF6,CH3CN溶液中的循环伏安图:聚[4,8-二(十二烷氧基)-苯并[1,2-b;3,4-b]二噻吩-2,6-二基]-共-[3,4-乙撑二氧基噻吩-2,5-二基](具有实心方形的线)、聚[4,8-二(十二烷氧基)-苯并[1,2-b;3,4-b]二噻吩-2,6-二基]-共-[(E)-1,2-亚乙烯基](具有空心方形的线)、聚[4,8-二(十二烷氧基)-苯并[1,2-b;3,4-b]二噻吩-2,6-二基]-共-[噻吩-2,5-二基](具有实心三角形的线)、聚[4,8-二(十二烷氧基)-苯并[1,2-b;3,4-b]二噻吩-2,6-二基]-共-[苯并[c][1,2,5]硒二唑-4,7-二基](具有空心三角形的线),以及聚[4,8-二(十二烷氧基)-苯并[1,2-b;3,4-b]二噻吩-2,6-二基]-共-[5,5′-(2,2′-(4,7-苯并[c][1,2,5]噻二唑-二基)-双(3-己基噻吩)-二基)(具有实心圆形的线);和
图8显示了具有结构ITO/PEDOT:PSS/聚[4,8-二(十二烷氧基)-苯并[1,2-b;3,4-b]二噻吩-2,6-二基]-共-[噻吩-2,5-二基]/PCBM(1∶1 wt/wt)/Ca/Al的聚合物太阳能电池器件的I-V曲线。
详述
在描述本发明的实施方案时,为了清楚起见,使用特定的术语。然而,本发明无意于局限于所选择的特定术语。应了解每个特定元件包括以类似的方式运行以实现类似目的的所有技术等同物。
用于聚合物太阳能电池的共轭聚合物材料应具有高迁移率,因此共轭聚合物的主链应具有根据本发明的一些实施方案的平面结构。这也能有助于形成π-π堆积结构并促进两个相邻主链之间的电荷转移。这类材料应具有低带隙以提供良好的太阳光捕集;它们也应具有与聚合物太阳能电池器件中的电极和电子受体材料相匹配的适当的分子能级。因此根据本发明的一些实施方案,期望的是提供具有一部分或全部上述性质的共轭聚合物作为光伏材料。
定义和命名:
除非另外指出,否则本发明不局限于特定的原料、试剂或反应条件,而是可以变化。本文所用的术语“烷基”指支化的或未支化的饱和烃基,其通常但并非必需地含有1至24个碳原子,如甲基、乙基、正丙基、异丙基、正辛基、异辛基、癸基等;以及环烷基,如环戊基、环己基等。
“亚芳基”具有其通常含义。本文所用的术语“杂亚芳基”指含有一个或更多个“杂原子”(即除了碳之外的原子,例如氮、氧、硫、硅、硒、磷)的具有5或6个原子的芳环。本文所用的术语“含N杂亚芳基”指其中如上定义的一个或更多个“杂原子”为氮的杂亚芳基。“稠合的”环共用相同的键,“连接的”环通过单键连接。
如“取代的亚芳基”、“取代的杂亚芳基”等中的术语“取代的”指结合至碳或杂原子的至少一个氢原子被一个或更多个非氢取代基所取代的部分。这样的取代基可包括但不限于烷基或芳基以及如卤素、羟基、烷基硫代、烷氧基、芳氧基、烷基羰基、酰氧基、硝基、氰基等的官能团。
根据本发明的一些实施方案的新型聚合物如下:
根据本发明的一些实施方案的聚合物包括具有式(I)的一般结构的重复单元:
其中A1、A2、R1和R2独立地选自氢;具有至多18个C原子的烷基和烷氧基、氰基、硝基、芳基和取代芳基。Ar可为取代的或未取代的亚乙烯基;亚乙炔基;单环、双环和多环亚芳基;单环、双环和多环杂亚芳基;或者稠合或连接的1至5个这样的上述基团、通常1至3个这样的基团。当被取代时,Ar基团可具有1或2个取代基,所述取代基独立地为芳基、具有1-18个碳原子的烷基和烷氧基,或者在Ar基团上的两个相邻碳原子可被取代以一起形成乙撑二氧基。
在一些实施方案中,Ar为具有独立地选自氮、硫和硒的1至6个杂原子的单环、双环或三环杂亚芳基,其中Ar任选地被苯基、烷基、硝基或乙撑二氧基取代。在一些实施方案中,Ar为任选地稠合至亚芳基或杂亚芳基的含有S的单环杂亚芳基。在一些实施方案中,Ar为含有1至4个氮原子的单环杂亚芳基,其任选地含有1或2个硫原子,并任选地稠合至一个或更多个亚芳基或杂亚芳基。在其他实施方案中,Ar为未取代的。本发明的实施方案包括其中R1=R2=十二烷氧基的化合物。在其他实施方案中,R1=R2=十二烷氧基且A1=A2=H。
合适的Ar部分的实例包括但不限于如下单元或取代的如下单元:
在如上结构中,R是碳原子数为1-18的烷基。
本发明的实施方案包括其中Ar为如下基团之一的那些:
2,3-二苯基喹喔啉-5,8-二基;
2,1,3-苯并噻二唑-4,7-二基;
噻吩并[3,4-b]吡嗪-5,7-二基;
3,4-乙撑二氧基噻吩-2,5-二基;
(E)-1,2-亚乙烯基噻吩-2,5-二基;
苯并[c][1,2,5]硒二唑-4,7-二基;
5,5′-(2,2′-(4,7-苯并[c][1,2,5]噻二唑-二基)-双(3-己基噻吩)-二基;或噻吩-2,5-二基。
在实施方案中,式(I)的化合物为如下化合物之一:
聚[4,8-二(十二烷氧基)-苯并[1,2-b;3,4-b]二噻吩-2,6-二基]-共-[2,3-二苯基喹喔啉-5,8-二基];
聚[4,8-二(十二烷氧基)-苯并[1,2-b;3,4-b]二噻吩-2,6-二基]-共-[2,1,3-苯并噻二唑-4,7-二基];
聚[4,8-二(十二烷氧基)-苯并[1,2-b;3,4-b]二噻吩-2,6-二基]-共-[噻吩并[3,4-b]吡嗪-5,7-二基];
聚[4,8-二(十二烷氧基)-苯并[1,2-b;3,4-b]二噻吩-2,6-二基]-共-[3,4-乙撑二氧基噻吩-2,5-二基];
聚[4,8-二(十二烷氧基)-苯并[1,2-b;3,4-b]二噻吩-2,6-二基]-共-[(E)-1,2-亚乙烯基];
聚[4,8-二(十二烷氧基)-苯并[1,2-b;3,4-b]二噻吩-2,6-二基]-共-[噻吩-2,5-二基];
聚[4,8-二(十二烷氧基)-苯并[1,2-b;3,4-b]二噻吩-2,6-二基]-共-[苯并[c][1,2,5]硒二唑-4,7-二基];
聚[4,8-二(十二烷氧基)-苯并[1,2-b;3,4-b]二噻吩-2,6-二基]-共-[5,5′-(2,2′-(4,7-苯并[c][1,2,5]噻二唑-二基)-双(3-己基噻吩)-二基];或
聚[4,8-二(十二烷氧基)-苯并[1,2-b;3,4-b]二噻吩-2,6-二基]-共-[3,4-乙撑二氧基噻吩-2,5-二基]。
式(I)的聚合物的一些实施方案包括具有式(II)的结构的重复单元:
其中:R1、R2和Ar如上所定义。在该实施方案中,当期望提高的溶解度时,一些更具体的实例为其中R1和R2选自具有4-12个碳原子的烷基或具有4-12个碳原子的烷氧基且Ar为含N杂亚芳基的聚合物。在示例性的实施方案中,R1和R2独立地选自具有至多18个碳原子的烷基和具有至多18个碳原子的烷氧基,且Ar为如下所示的单元或取代的如下所示的单元之一:
在另一实施方案中,式(I)的聚合物包括具有式(III)的结构的重复单元:
其中:R1、R2、R3和R4独立地选自具有至多18个碳原子的烷基或具有至多18个碳原子的烷氧基;Ar1为含N杂亚芳基。示例性的含N杂亚芳基包括但不限于如下单元,或取代的如下单元:
在根据式(III)的化合物的一些实施方案中,例如当期望提高的溶解度时,R1和R2可以是相同或不同的具有4-12个碳原子的烷基。
通常,聚合物的数均分子量为约1000至1,000,000,该聚合物可进一步具有约5000至500,000的数均分子量,并可进一步具有约20,000至200,000的数均分子量。应理解可改变分子量以优化聚合物性质。例如,较低的分子量可确保溶解度,而较高的分子量可确保良好的成膜性质。聚合:
根据本发明的一些实施方案的聚合物通常通过共聚具有式(IV)和式(V)的结构的单体而合成,
其中在式(IV)和式(V)中:R1、R2、A1、A2和Ar如上所定义;X依赖于Y进行选择。若Y选自包括但不限于1,3,2-二氧杂硼烷-2-基、4,4,5,5-四甲基-1,3,2-二氧杂环戊硼烷(dioxaborolane)-2-基和5,5-二甲基-1,3,2-二氧杂硼烷-2-基的硼酸基团或硼酸酯基团,或包括氯化镁、溴化镁和碘化镁在内的卤化镁基团,或包括氯化锌和溴化锌在内的卤化锌基团,或包括但不限于三甲基锡、三乙基锡和三丁基锡在内的三烷基锡基团时,X应当选自I、Br或Cl,并且如果Y选自I、Br或Cl,则X应当选自包括但不限于1,3,2-二氧杂硼烷-2-基、4,4,5,5-四甲基-1,3,2-二氧杂环戊硼烷-2-基和5,5-二甲基-1,3,2-二氧杂硼烷-2-基的硼酸基团或硼酸酯基团,或包括氯化镁、溴化镁和碘化镁在内的卤化镁基团,或包括氯化锌和溴化锌在内的卤化锌基团,或包括但不限于三甲基锡、三乙基锡和三丁基锡在内的三烷基锡基团。
使用上述式(IV)和(V)的单体的根据本发明的一些实施方案的聚合物的聚合路线如以下方案梭表示:
其中:A1、A2、R1、R2、Ar、X和Y如上所定义。
若在二镁卤代芳烃化合物和芳烃二卤化物化合物之间进行缩聚反应,则该聚合反应为如McCullough和Lowe所报道的典型的‘McCullough法’[J.Chem.Soc,Chem.Commun.1992,70]。在McCullough法中,THF通常用作溶剂,有时也可使用甲苯和THF的混合物。含有Pd或Ni的一些催化剂,例如[1,3-双(二苯基膦基)丙烷]二氯镍(II)和四(三苯基膦)钯(0),可用作该反应的催化剂,且催化剂与原料之间的摩尔比为10-0.1%。所述反应通常在约10℃至溶剂的回流点下进行。取决于反应物的反应性,聚合可进行30分钟至24小时。在该反应中所用的二镁卤代芳烃可由如Loewe和McCullough报道的Grignard置换反应[Macromolecules,2001,(34),4324-4333],或由芳烃二卤化物和镁之间的反应制得。在一些实施方案中,在用于本发明的聚合物的‘McCullough法’中所用的芳烃二卤化物和二镁卤代芳烃为芳烃二溴化物和二镁溴代芳烃。
若在二锌卤代芳烃化合物和芳烃二卤化物化合物之间进行缩聚反应,则该聚合反应为如Chen和Rieke所报道的典型的‘Rieke法’[Synth.Met.1993,(60),175.]。在该方法中,THF通常用作溶剂,一些含有Pd或Ni的催化剂,例如[1,2-双(二苯基膦)乙烷]二氯镍(II),可用作该反应的催化剂,且催化剂与原料的摩尔比为10-0.1%。所述反应通常在约10℃至溶剂的回流点下进行。取决于反应物的反应性,聚合可进行30分钟至24小时。在优选的实施方案中,在用于本发明的聚合物的‘Rieke法’中所用的芳烃二卤化物和二锌卤代芳烃为芳烃二溴化物和二锌氯代芳烃。
若在双(三烷基甲锡烷基)芳烃化合物和芳烃二卤化物之间进行缩聚反应,则该聚合反应为如Iraqi和Barker所报道的典型的‘Stille偶联法’[J.Mater.Chem.1998,(8)25]。在该方法中,包括但不限于四氢呋喃(THF)、二甲基甲酰胺(DMF)和甲苯的许多类型的溶剂通常可用作溶剂,含有Pd的一些催化剂,例如四(三苯基膦)钯(0),可用作该反应的催化剂,且催化剂和原料之间的摩尔比为10-0.1%。所述反应通常在约60℃至溶剂的回流点下进行。取决于反应物的反应性,聚合可进行1至72小时。在一些实施方案中,在用于本发明的聚合物的‘Stille偶联法’中所用的芳烃二卤化物和二锌卤代芳烃为芳烃二溴化物和二锌氯代芳烃。
若在芳烃二硼酸化合物或芳烃二硼酸酯化合物和芳烃二卤化物之间进行缩聚反应,则该聚合反应为如Miyaura和Suzuki报道的典型的‘Suzuki反应’[Chemical reviews 1995(95):2457-2483]。在该方法中,包括但不限于THF和甲苯的许多类型的溶剂通常可用作溶剂,含有Pd的一些催化剂,例如四(三苯基膦)钯(0),可用作该反应的催化剂,且催化剂和原料之间的摩尔比为10-0.1%。所述反应通常在约60℃至溶剂的回流点下进行。取决于反应物的反应性,聚合可进行12至72小时。在一些实施方案中,在用于本发明的一些实施方案的聚合物的‘Suzuki反应’中所用的芳烃二卤化物为芳烃二溴化物或二锌氯代芳烃。
通常,根据本发明的一些实施方案的聚合物可用于其中共轭聚合物,特别是共轭光伏聚合物具有效用的任意应用中。例如,本发明的聚合物可适于作为如下器件中的活性材料:薄膜半导体器件如太阳能电池、发光二极管、晶体管、光检测器和光导体;电化学器件如可充电电池、电容器、超级电容器和电致变色器件,以及传感器。
可制备半导体组合物,其包含任选地与掺加剂组合的根据本发明的一个实施方案的聚合物,所述掺加剂通常为一种化合物,选择该化合物使得当包括光或电压的激发源施加至该组合物时,在掺加剂和聚合物之间发生电荷转移和/或能量转移。例如,所述掺加剂可为富勒烯,如:C60、C70或C80,或一些取代的富勒烯化合物,如PCBM([6,6]-苯基C61丁酸甲酯)和PCBB([6,6]-苯基C61丁酸丁酯)。根据本发明的一些实施方案的聚合物特别地可用作如光检测器器件、太阳能电池器件等的光伏器件中的光伏材料。光伏器件,包括太阳能电池器件,通常包括在空穴收集电极层和电子收集层之间的合适的光伏材料的层合体。另外的层、元件或衬底可存在或可不存在。
图1为根据本发明的一个实施方案的光电器件100的示意图。该光电器件100具有第一电极102、与第一电极102间隔开的第二电极104,和在第一电极和第二电极之间设置的活性层106。例如,该光电器件100可在电极和活性层之间具有多个活性材料层和/或材料层,例如层108。所述活性层可包含根据本发明的一个或更多个实施方案的共轭聚合物材料。在本发明的一些实施方案中,电极102和104之一或两者可为透明电极。
图2为根据本发明的另一实施方案的光电器件200的示意图。该光电器件200具有第一电极202、与第一电极202间隔开的第二电极204,和在第一电极和第二电极之间设置的活性层206。该实施方案为在第一电极202和第二电极204之间具有第二活性层210的光电器件的实例。该光电器件200可在活性层和电极之间和/或在两个活性层之间具有另外的材料层。例如,在活性层206和210之间可存在层208。根据本发明的器件不局限于仅有一个或两个活性层;在本发明的一些实施方案中,它们可具有多个活性层。图1和2的示意图作为实例显示。根据本发明的其他实施方案的器件不限于这些特定的实例。
实验
本发明的实践可采用本领域技术内的聚合物化学的常规技术。在以下实施例中,努力确保所用数字(包括量、温度、反应时间等)的准确性,但应考虑一些实验误差和偏差。在以下实施例中所用的温度以℃表示,压力为大气压或接近大气压。所有的溶剂都是以HPLC级购得,并且所有反应在氩气惰性气氛下常规进行。除非另外指出,否则所有试剂都是商业获得的。
实施例1
2,6-双(三甲基甲锡烷基)-4,8-二(十二烷氧基)-苯并[1,2-b:4,5-b′]二噻吩的合成
将根据Beimling公开的方法[Chem.Ber.1986;(119)3198-3203.]合成的4,8-二氢苯并[1,2-b:4,5-b′]二噻吩-4,8-二酮(dion)、锌粉(2.86g,44mmol)和60ml水放入250ml烧瓶中,然后加入12g NaOH。将该混合物良好搅拌并加热至回流,保持1小时。然后,将1-溴-十二烷(15g,60mmol)和催化量的四丁基溴化铵加入所述烧瓶。反应物回流6小时,并倒入冷水,用200ml乙醚萃取2次。醚层用无水MgSO4干燥。在去除溶剂之后,通过从乙醇重结晶2次纯化粗产物。获得作为无色晶体的9.26g4,8-二(十二烷氧基)-苯并[1,2-b;3,4-b]二噻吩。1H NMR(CDCl3):7.66(d,2H),7.47(d,2H),4.26(t,4H),1.87(五重峰,4H),1.53(m,4H),1.37-1.27(m,32H),0.88(t,6H)。
在250ml烧瓶中,将4,8-二(十二烷氧基)-苯并[1,2-b;3,4-b]二噻吩(5.58g,10mmol)溶解于100ml二氯甲烷中。将溴(3.2g,20mmol)溶解于在漏斗中的60ml二氯甲烷中,并缓慢滴入在冰水浴中的烧瓶中,然后在环境温度下搅拌反应物4-6小时。所有的挥发性物质在真空下去除。残余物用己烷重结晶2次。获得作为白色固体的6.37g 2,6-二溴-4,8-二(十二烷氧基)-苯并[1,2-b;3,4-b]二噻吩。1H NMR(CDCl3):7.43(s,2H),4.17(t,4H),1.83(五重峰,4H),1.54(m,4H),1.36-1.27(m,32H),0.89(t,6H)。
将2,6-二溴-4,8-二(十二烷氧基)-苯并[1,2-b;3,4-b]二噻吩(4.30g,6mmol)和100ml THF加入在惰性气氛下的烧瓶中。通过液氮-丙酮浴将溶液冷却至-78℃,逐滴加入4.55ml正丁基锂(13.2mmol,在正己烷中2.9M)。在-78℃下搅拌1小时之后,在烧瓶中出现大量白色固体沉淀。然后,一次加入14mmol三甲基氯化锡(14ml,在正己烷中1M),反应物迅速变得澄清。移开冷却浴,在环境温度下搅拌反应物2小时。然后,将其倒入200ml冷水中,用醚萃取3次。有机层用水洗涤2次,然后用无水MgSO4干燥。在真空下去除溶剂之后,残余物用乙醇重结晶2次。获得作为无色针状晶体的6.7g 2,6-双(三甲基锡)-4,8-二(十二烷氧基)-苯并[1,2-b;3,4-b]二噻吩。
实施例2
聚[4,8-二(十二烷氧基)-苯并[1,2-b;3,4-b]二噻吩-2,6-二基]-共-[2,3-二苯基喹喔啉-5,8-二基]的合成
将5,8-二溴-2,3-二苯基喹喔啉(0.44g,1mmol,根据Chen[J.Am.Chem.Soc;2006,(128)10992-10993]制得)、2,6-双(三甲基锡)-4,8-二(十二烷氧基)-苯并[1,2-b;3,4-b]-二噻吩,和50ml甲苯放入带有油浴的双口烧瓶中。溶液用氩气吹扫10分钟,然后将20mg Pd(PPh3)4加入烧瓶中。再次吹扫溶液20分钟。小心地将油浴加热至110℃,在氩气氛下在该温度下搅拌反应物16小时。然后,将反应物冷却至室温,通过加入100ml甲醇使聚合物沉淀,并通过Soxhlet套管过滤,然后用甲醇、己烷和氯仿进行Soxhlet萃取。通过旋转蒸发从氯仿馏分回收作为固体样品的聚合物。该固体在真空下干燥1天,得到最终产物。
实施例3
聚-2,6-(4,8-二(十二烷氧基)-苯并[1,2-b;3,4-b]二噻吩)的合成
按照实施例2的程序,不同的是使用0.71g 2,6-二溴-4,8-二(十二烷氧基)-苯并[1,2-b;3,4-b]二噻吩来代替5,8-二溴-2,3-二苯基喹喔啉。
实施例4
聚[4,8-二(十二烷氧基)-苯并[1,2-b;3,4-b]二噻吩-2,6-二基]-共-[2,1,3-苯并噻二唑-4,7-二基]的合成
按照实施例2的程序,不同的是使用0.294g 4,7-二溴-2,1,3-苯并噻二唑(根据Fabiana S Mancilha,[J.Org.Chem.;2006;(21)4924-4933]制得)来代替5,8-二溴-2,3-二苯基喹喔啉。
实施例5
聚[4,8-二(十二烷氧基)-苯并[1,2-b;3,4-b]二噻吩-2,6-二基]-共-[噻吩并[3,4-b]吡嗪-5,7-二基]的合成
将噻吩并[3,4-b]吡嗪(0.272g,2mmol,根据Kenning[J.Org.Chem.,2002,(67),9073-9076]制得)溶解于20ml二甲基甲酰胺中,然后加入0.712g N-溴代-琥珀酰胺。反应物在环境温度下搅拌2小时。加入50ml水,混合物用100ml乙醚萃取3次。在去除溶剂之后,通过硅胶柱使用二氯甲烷作为洗脱液纯化粗产物,获得作为黄色固体的5,7-二溴-噻吩并[3,4-b]吡嗪。
然后,按照实施例2的程序,不同的是使用0.294g 5,7-二溴-噻吩并[3,4-b]吡嗪来代替5,8-二溴-2,3-二苯基喹喔啉。
实施例6
聚[4,8-二(十二烷氧基)-苯并[1,2-b;3,4-b]二噻吩-2,6-二基]-共-[3,4-乙撑二氧基噻吩-2,5-二基]的合成
按照实施例2的程序,不同的是使用0.294g 2,5-二溴-3,4-乙撑二氧基噻吩(根据Robin G.Hicks,[J.Am.Chem.Soc;122;28;2000;6746-6753.]制得)来代替5,8-二溴-2,3-二苯基喹喔啉。
实施例7
聚[4,8-二(十二烷氧基)-苯并[1,2-b;3,4-b]二噻吩-2,6-二基]-共-[(E)-1,2-亚乙烯基]的合成
按照实施例2的程序,不同的是使用0.626g(E)-1,2-双(三丁基甲锡烷基)乙烯(根据Jianhui Hou和Yongfang Li,[Macromolecules,39(14),4657-4662,2006]制得)来代替2,6-双(三甲基锡)-4,8-二(十二烷氧基)-苯并[1,2-b;3,4-b]二噻吩,且使用2,6-二溴-4,8-二(十二烷氧基)-苯并[1,2-b;3,4-b]二噻吩(0.716g,1mmol)来代替5,8-二溴-2,3-二苯基喹喔啉。
实施例8
聚[4,8-二(十二烷氧基)-苯并[1,2-b;3-b]二噻吩-2,6-二基]-共-[噻吩2,5-二基]的合成
按照实施例2的程序,不同的是使用0.716g 2,6-二溴-4,8-二(十二烷氧基)-苯并[1,2-b;3,4-b]二噻吩来代替5,8-二溴-2,3-二苯基喹喔啉,且使用0.662g(E)-1,2-双(三丁基甲锡烷基)噻吩(根据Jianhui Hou和Yongfang Li,[J.Am.Chem.Soc,128(14),4911-4916,2006.]制得)来代替2,6-双(三甲基锡)-4,8-二(十二烷氧基)-苯并[1,2-b;3,4-b]二噻吩。
实施例9
聚[4,8-二(十二烷氧基)-苯并[1,2-b;3,4-b]二噻吩-2,6-二基]-共-[苯并[c][1,2,5]硒二唑-4,7-二基]的合成
按照实施例2的程序,不同的是使用0.294g 4,7-二溴苯并[c][1,2,5]硒二唑(根据Martin R.Bryce[J.Chem.Soc.Perkin Trans.1981,(1)607-613]制得)来代替5,8-二溴-2,3-二苯基喹喔啉。
实施例10
聚[4,8-二(十二烷氧基)-苯并[1,2-b;3,4-b]二噻吩-2,6-二基]-共-[5,5′-(2,2′-(4,7-苯并[c][1,2,5]噻二唑-二基)-双(3-己基噻吩)-二基]的合成
按照实施例2的程序,不同的是使用0.627g 4,7-双(5-溴-3-己基噻吩-2-基)-苯并[c][1,2,5]噻二唑来代替5,8-二溴-2,3-二苯基喹喔啉。
实施例11
可加工性和利用吸收光谱的光学带隙的测量
在实施例2、3、4、5、6、7、8、9和10中制得的聚合物与各种有机溶剂混合,所述有机溶剂包括氯化溶剂,如氯仿、二氯甲烷、氯苯和二氯苯,以及其他溶剂,如甲醇、甲苯、四氢呋喃。发现在实施例1、2、4、5、6、7、8和9中制得的聚合物在氯化溶剂中具有良好的溶解度,但在甲醇中不可溶。通过将聚合物溶液旋涂至玻璃片上而制得高品质薄膜。发现在实施例3中制得的聚合物在环境温度下在所有溶剂中都不可溶,但在75℃以上在甲苯和氯苯中具有良好的溶解度。
聚合物膜的测得的吸收光谱示于图3、4和5中。聚合物的光学带隙使用经验公式(Eg=1240/λ最大,其中:Eg为聚合物的光学带隙;λ最大为吸收光谱在长波长方向的起始点)计算并示于表1中。
实施例12
利用电化学循环伏安法的最高占据分子轨道(HOMO)测量
使用根据Yongfang Li[Synth.Met,1999,(99)],243.]的方法测定聚合物的HOMO能级。将在实施例1中制得的聚合物(2.0mg)溶解于1ml甲苯中,然后使一小滴该溶液落(cast)至用作工作电极的铂板电极上;使用0.1mol/L Bu4NPF6,CH3CN溶液作为支持电解质;使用铂作为对电极;使用银丝作为半参比电极。电化学循环伏安法测量在该体系中进行。重复相同的程序以确定本发明的其他聚合物的HOMO能级。本发明的聚合物的循环伏安数据示于图6和7中,本发明的聚合物的HOMO能级数据示于表1中。
实施例13
聚合物太阳能电池器件的开路电压
将在实施例2、3、4、5、6、7、8、9和10中制得的聚合物之一(30mg)溶解于氯苯中以制得20mg ml-1的溶液,然后与50wt.%的PCBM共混。在透明氧化铟锡(ITO)涂布的玻璃衬底上制造聚合物太阳能电池。将导电聚合物聚(苯乙烯磺酸酯)掺杂的聚(3,4-乙撑二氧基噻吩)(PEDOT:PSS)的薄层旋涂至ITO表面以得到更好的界面。使用Dektek表面光度仪测得的PEDOT:PSS层的厚度为约30nm。然后,使用如上制得的溶液旋涂薄层。然后,在大约10-4Pa的压力下相继蒸镀钙和铝的薄层。在填充N2的手套箱中在使用氙灯太阳模拟器的AM 1.5G辐照(100mW cm-2)下进行测试,所述氙灯太阳模拟器在国家可再生能源实验室(NREL)中使用硅二极管(具有KG5可见滤光器)校正。
聚合物太阳能电池器件的开路电压示于表1中。由于聚合物的不同HOMO能级,基于本发明的聚合物的器件的开路电压由0.1V变化至0.96V。
实施例14
基于聚[4,8-二(十二烷氧基)-苯并[1,2-b;3,4-b]二噻吩-2,6-二基]-共-[噻吩-2,5-二基]/PCBM(1∶1 wt/wt)的聚合物太阳能电池器件的光伏性质
按照实施例13的程序制造并表征聚合物太阳能电池器件。器件的I-V曲线示于图8中。
本发明参照特定的实施方案和实施例进行描述。然而,本发明不局限于仅仅所述的实施方案和实施例。本领域普通技术人员应认识到,基于本文的教导,在不偏离权利要求书所限定的本发明的范围下可进行许多改变和替代。
表1.聚合物膜的光吸收和循环伏安结果
Claims (12)
1.一种含有重复单元的共轭聚合物,其中所述重复单元具有式(III)的结构:
其中R1、R2、R3和R4独立地选自具有至多18个碳原子的烷基或具有至多18个碳原子的烷氧基,并且
其中Ar1选自如下所示的单元或取代的如下所示的单元:
2.根据权利要求1所述的共轭聚合物,其中Ar1选自如下所示的单元或取代的如下所示的单元:
3.根据权利要求1所述的共轭聚合物,其为:
聚[4,8-二(十二烷氧基)-苯并[1,2-b;3,4-b]二噻吩-2,6-二基]-共-[5,5′-(2,2′-(4,7-苯并[c][1,2,5]噻二唑-二基)-双(3-己基噻吩)-二基]。
4.根据权利要求1所述的共轭聚合物,其中R1=R2=十二烷氧基。
5.一种电子器件或光电器件,其包含根据权利要求1或2所述的共轭聚合物材料。
6.根据权利要求5所述的器件,其中所述共轭聚合物材料为光伏材料。
7.根据权利要求6所述的器件,其中所述电子器件或光电器件为聚合物太阳能电池器件或光检测器器件。
8.根据权利要求7所述的器件,其中所述器件为包含本体异质结结构的聚合物太阳能电池器件。
9.根据权利要求8所述的器件,其中所述本体异质结结构包含除了所述共轭聚合物之外的至少一种成分。
10.根据权利要求9所述的器件,其中除了所述共轭聚合物之外的所述至少一种成分为选自富勒烯或其衍生物中的至少一种。
11.根据权利要求10所述的器件,其中所述富勒烯或其衍生物为[6,6]-苯基C61丁酸甲酯或[6,6]-苯基C71丁酸甲酯的至少一种。
12.一种电子器件或光电器件,其包括:
第一电极;
与所述第一电极间隔开的第二电极;和
在所述第一电极和所述第二电极之间设置的活性材料层,
其中所述活性层含有根据权利要求1或2所述的包含重复单元的共轭聚合物。
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Families Citing this family (54)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8334456B2 (en) * | 2009-05-21 | 2012-12-18 | Polyera Corporation | Conjugated polymers and their use in optoelectronic devices |
US8372945B2 (en) | 2009-07-24 | 2013-02-12 | Solarmer Energy, Inc. | Conjugated polymers with carbonyl substituted thieno[3,4-B]thiophene units for polymer solar cell active layer materials |
EP2470584A4 (en) | 2009-08-28 | 2014-01-22 | Agency Science Tech & Res | POLYMAL SEMICONDUCTORS AND DEVICES THEREFOR AND METHOD THEREFOR |
CN102549791B (zh) | 2009-08-28 | 2015-01-07 | 新加坡科技研究局 | 双极性聚合物半导体材料及有机电子器件 |
CN102597046A (zh) * | 2009-10-29 | 2012-07-18 | 住友化学株式会社 | 高分子化合物及电子元件 |
WO2011085004A2 (en) * | 2010-01-05 | 2011-07-14 | Konarka Technologies, Inc. | Photovoltaic cell with benzodithiophene-containing polymer |
US8304512B2 (en) * | 2010-01-19 | 2012-11-06 | Xerox Corporation | Benzodithiophene based materials compositions |
US10050201B2 (en) | 2010-04-19 | 2018-08-14 | Merck Patent Gmbh | Polymers of benzodithiophene and their use as organic semiconductors |
WO2011147067A1 (zh) * | 2010-05-24 | 2011-12-01 | 海洋王照明科技股份有限公司 | 含稠环噻吩单元喹喔啉共轭聚合物及其制备方法和应用 |
US9184390B2 (en) | 2010-06-08 | 2015-11-10 | The University Of North Carolina At Chapel Hill | Polymers with tunable band gaps for photonic and electronic applications |
CN102906151B (zh) * | 2010-06-25 | 2014-05-07 | 海洋王照明科技股份有限公司 | 基于苯唑二噻吩和噻吩并吡嗪的共轭聚合物及其制备方法和应用 |
DE102010032737A1 (de) * | 2010-07-29 | 2012-02-02 | Merck Patent Gmbh | Polymere enthaltend substituierte Benzodithiopheneinheiten, Blends enthaltend diese Polymere sowie Vorrichtungen enthaltend diese Polymere oder Blends |
US8993711B2 (en) * | 2010-10-06 | 2015-03-31 | Polyera Corporation | Semiconducting polymers and optoelectronic devices incorporating same |
KR102011872B1 (ko) | 2011-01-04 | 2019-08-19 | 삼성전자주식회사 | 낮은 밴드 갭을 갖는 유기 반도체 화합물 및 이를 포함하는 트랜지스터와 전자 소자 |
DE102011119900A1 (de) | 2011-01-21 | 2012-07-26 | Merck Patent Gmbh | Flüssigkristalline Medien, Bauteile für die Hochfrequenztechnik und mesogene Verbindungen |
US8742403B2 (en) | 2011-03-08 | 2014-06-03 | Samsung Electronics Co., Ltd. | Xanthene based semiconductor compositions |
JP2014518564A (ja) * | 2011-04-21 | 2014-07-31 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング | 共役ポリマー |
CN103534259A (zh) | 2011-05-16 | 2014-01-22 | 默克专利股份有限公司 | 共轭聚合物 |
JP6101264B2 (ja) * | 2011-07-21 | 2017-03-22 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツングMerck Patent Gesellschaft mit beschraenkter Haftung | 共役ポリマー |
JP6074996B2 (ja) * | 2011-10-21 | 2017-02-08 | 東レ株式会社 | 光起電力素子用材料および光起電力素子 |
JP2015505580A (ja) * | 2012-02-03 | 2015-02-23 | ザ・ユニバーシティ・オブ・シカゴThe University Of Chicago | 半導体ポリマー |
US9006568B2 (en) | 2012-02-15 | 2015-04-14 | Phillips 66 Company | Synthesis of photovoltaic conjugated polymers |
TWI635111B (zh) | 2012-03-16 | 2018-09-11 | 馬克專利公司 | 共軛聚合物 |
CN103456510B (zh) * | 2012-06-01 | 2016-04-13 | 国家纳米科学中心 | 一种超级电容器的电极材料 |
WO2014007867A1 (en) * | 2012-07-02 | 2014-01-09 | The Regents Of The University Of California | Semi-transparent, transparent, stacked and top-illuminated organic photovoltaic devices |
US8703960B2 (en) | 2012-08-23 | 2014-04-22 | Phillips 66 Company | Benzobisthiazole building blocks for conjugated polymers |
US8895751B2 (en) | 2012-08-23 | 2014-11-25 | Phillips 66 Company | Process of manufacturing benzobisthiazole building blocks for conjugated polymers |
CN102816304B (zh) * | 2012-08-30 | 2014-12-10 | 西安近代化学研究所 | 9-辛基咔唑与氟代喹喔啉的共轭聚合物 |
CN102816299B (zh) * | 2012-08-30 | 2014-10-15 | 西安近代化学研究所 | 4,8-二异辛烷氧基苯基[1,2-b:4,5-b’]联噻吩及氟代喹喔啉的共轭聚合物 |
CN102827358B (zh) * | 2012-08-30 | 2014-10-15 | 西安近代化学研究所 | 4,8-二(5-异辛基噻吩)苯基[1,2-b:4,5-b’]联噻吩及氟代喹喔啉的共轭聚合物 |
CN102838732B (zh) * | 2012-08-30 | 2014-10-15 | 西安近代化学研究所 | 4,8-二异辛烷氧基苯基[1,2-b:4,5-b’]联噻吩及氟代喹喔啉的共轭聚合物 |
CN103730581B (zh) * | 2012-10-15 | 2016-05-18 | 乐金显示有限公司 | 有机发光装置和使用其的有机发光显示装置 |
WO2014088795A1 (en) | 2012-12-03 | 2014-06-12 | Phillips 66 Company | Benzo [1,2-b:4,5-b'] dithiophene-thienothiophene based conjugated polymers |
US9045596B2 (en) * | 2013-02-05 | 2015-06-02 | Phillips 66 Company | Method of purifying conjugated polymers |
CN104177593A (zh) * | 2013-05-28 | 2014-12-03 | 海洋王照明科技股份有限公司 | 含喹喔啉基的聚合物及其制备方法和有机太阳能电池器件 |
WO2014205512A1 (en) * | 2013-06-25 | 2014-12-31 | The University Of Melbourne | Novel polymers and their use in organic photovoltaics |
US9680101B2 (en) * | 2013-07-31 | 2017-06-13 | Lg Chem, Ltd. | Copolymer and organic solar cell comprising same |
EP3066147A2 (en) * | 2013-11-06 | 2016-09-14 | Merck Patent GmbH | Conjugated polymers |
WO2016078744A1 (en) * | 2014-11-19 | 2016-05-26 | Merck Patent Gmbh | Semiconducting mixtures |
US11554576B2 (en) * | 2017-01-26 | 2023-01-17 | Face International Corporation | Energy harvesting methods for providing autonomous electrical power to mobile devices |
US10312448B2 (en) | 2015-10-01 | 2019-06-04 | Phillips 66 Company | Process of manufacturing an electron transport material |
US9911919B2 (en) | 2015-10-01 | 2018-03-06 | Phillips 66 Company | Process of manufacturing an electron transport material |
WO2017058406A1 (en) | 2015-10-01 | 2017-04-06 | Phillips 66 Company | Formation of films for organic photovoltaics |
US9905769B2 (en) | 2015-10-01 | 2018-02-27 | Phillips 66 Company | Process of manufacturing an electron transport material |
US10418555B2 (en) | 2015-10-01 | 2019-09-17 | Phillips 66 Company | Formation of films for organic photovoltaics |
CN105399930B (zh) * | 2015-12-24 | 2017-10-03 | 宁波源丰消防设备有限公司 | 一种用于有机半导体的共轭聚合物及其制备方法 |
CN107586379A (zh) * | 2016-07-07 | 2018-01-16 | 南方科技大学 | 含氯代苯并噻二唑的共轭聚合物及其制备方法和有机太阳能电池器件 |
WO2021041478A2 (en) * | 2019-08-27 | 2021-03-04 | Phillips 66 Company | Methods and systems of organic semiconducting polymers |
CN113583507A (zh) * | 2021-06-29 | 2021-11-02 | 成都灵睿奥创科技有限公司 | 一种有机半导体墨水、制备方法及应用 |
GB202117608D0 (en) * | 2021-12-06 | 2022-01-19 | Univ Oxford Innovation Ltd | Novel compounds |
CN114085362B (zh) * | 2021-12-06 | 2023-04-18 | 北京航空航天大学 | 一种含多元芳香环并噻吩二酮的聚合物给体材料的制备方法和应用 |
TWI826299B (zh) * | 2022-03-30 | 2023-12-11 | 天光材料科技股份有限公司 | 有機半導體混合物及其有機光電元件 |
CN115926119A (zh) * | 2022-11-25 | 2023-04-07 | 中国人民解放军96901部队25分队 | 一种宽波段吸收的电致变色聚合物及其制备方法和一种电致变色薄膜 |
CN116444798B (zh) * | 2023-03-29 | 2024-02-20 | 华南理工大学 | 一种含硒化合物和含硒聚合物的制备方法及其产物与应用 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101050221A (zh) * | 2006-04-04 | 2007-10-10 | 陈兆江 | 生产导电或发光聚合物有机配合体的噻吩衍生物及制备方法 |
EP1916250A1 (en) * | 2006-10-25 | 2008-04-30 | Xerox Corporation | Electronic devices comprising poly(dithienyl-benzodithiophenes) as semiconductors |
Family Cites Families (110)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3589946A (en) | 1968-09-06 | 1971-06-29 | Westinghouse Electric Corp | Solar cell with electrical contact grid arrangement |
US4060426A (en) | 1974-07-02 | 1977-11-29 | Polaroid Corporation | Tin indium oxide and polyvinylcarbazole layered polarized photovoltaic cell |
US4252573A (en) | 1975-06-06 | 1981-02-24 | University Of Delaware | Collector grid for CdS/CuS photovoltaic cells |
US4104084A (en) | 1977-06-06 | 1978-08-01 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Solar cells having integral collector grids |
US4400868A (en) | 1980-12-29 | 1983-08-30 | Varian Associates, Inc. | Method of making a transparent and electrically conductive bond |
DE3242791A1 (de) | 1982-11-19 | 1984-05-24 | Siemens AG, 1000 Berlin und 8000 München | Verfahren zum herstellen von elektrische kontakte bildende fingerelektrodenstrukturen an amorphen silizium-solarzellen |
US4586988A (en) | 1983-08-19 | 1986-05-06 | Energy Conversion Devices, Inc. | Method of forming an electrically conductive member |
US4528082A (en) | 1983-09-26 | 1985-07-09 | Exxon Research And Engineering Co. | Method for sputtering a PIN amorphous silicon semi-conductor device having partially crystallized P and N-layers |
US4590327A (en) | 1984-09-24 | 1986-05-20 | Energy Conversion Devices, Inc. | Photovoltaic device and method |
US4574160A (en) | 1984-09-28 | 1986-03-04 | The Standard Oil Company | Flexible, rollable photovoltaic cell module |
US4595790A (en) | 1984-12-28 | 1986-06-17 | Sohio Commercial Development Co. | Method of making current collector grid and materials therefor |
US4647711A (en) | 1985-01-29 | 1987-03-03 | The Standard Oil Company | Stable front contact current collector for photovoltaic devices and method of making same |
US4663495A (en) | 1985-06-04 | 1987-05-05 | Atlantic Richfield Company | Transparent photovoltaic module |
US4695674A (en) | 1985-08-30 | 1987-09-22 | The Standard Oil Company | Preformed, thin-film front contact current collector grid for photovoltaic cells |
US4680422A (en) | 1985-10-30 | 1987-07-14 | The Boeing Company | Two-terminal, thin film, tandem solar cells |
US4675468A (en) | 1985-12-20 | 1987-06-23 | The Standard Oil Company | Stable contact between current collector grid and transparent conductive layer |
US4686323A (en) | 1986-06-30 | 1987-08-11 | The Standard Oil Company | Multiple cell, two terminal photovoltaic device employing conductively adhered cells |
JPS63119586A (ja) | 1986-11-07 | 1988-05-24 | Sanyo Electric Co Ltd | 光起電力装置の製造方法 |
US4865999A (en) | 1987-07-08 | 1989-09-12 | Glasstech Solar, Inc. | Solar cell fabrication method |
EP0421133B1 (en) | 1989-09-06 | 1995-12-20 | Sanyo Electric Co., Ltd. | Manufacturing method of a flexible photovoltaic device |
US5133810A (en) | 1990-04-27 | 1992-07-28 | Sanyo Electric Co., Ltd. | Flexible photovoltaic device and manufacturing method thereof |
US5288338A (en) | 1990-05-23 | 1994-02-22 | Mitsubishi Denki Kabushiki Kaisha | Solar cell and method of producing the solar cell |
US5176758A (en) | 1991-05-20 | 1993-01-05 | United Solar Systems Corporation | Translucent photovoltaic sheet material and panels |
US5181968A (en) | 1991-06-24 | 1993-01-26 | United Solar Systems Corporation | Photovoltaic device having an improved collector grid |
FR2690279B1 (fr) | 1992-04-15 | 1997-10-03 | Picogiga Sa | Composant photovoltauique multispectral. |
FR2690278A1 (fr) | 1992-04-15 | 1993-10-22 | Picogiga Sa | Composant photovoltaïque multispectral à empilement de cellules, et procédé de réalisation. |
US5298086A (en) | 1992-05-15 | 1994-03-29 | United Solar Systems Corporation | Method for the manufacture of improved efficiency tandem photovoltaic device and device manufactured thereby |
US5331183A (en) * | 1992-08-17 | 1994-07-19 | The Regents Of The University Of California | Conjugated polymer - acceptor heterojunctions; diodes, photodiodes, and photovoltaic cells |
US5723873A (en) | 1994-03-03 | 1998-03-03 | Yang; Yang | Bilayer composite electrodes for diodes |
AUPM483494A0 (en) | 1994-03-31 | 1994-04-28 | Pacific Solar Pty Limited | Multiple layer thin film solar cells |
AU695669B2 (en) | 1994-05-19 | 1998-08-20 | Canon Kabushiki Kaisha | Photovoltaic element, electrode structure thereof, and process for producing the same |
DE19541417C2 (de) | 1995-11-07 | 1999-05-20 | L 3 Communications Elac Nautik | Vorrichtung zur Ultraschallbehandlung strömender Medien |
DE69736151T2 (de) | 1996-05-17 | 2007-05-10 | Canon K.K. | Photovoltaische Anordnung und Herstellungsverfahren |
US6325777B1 (en) | 1996-05-20 | 2001-12-04 | Medtronic Percusurge, Inc. | Low profile catheter valve and inflation adaptor |
US6469437B1 (en) | 1997-11-03 | 2002-10-22 | The Trustees Of Princeton University | Highly transparent organic light emitting device employing a non-metallic cathode |
US6420031B1 (en) | 1997-11-03 | 2002-07-16 | The Trustees Of Princeton University | Highly transparent non-metallic cathodes |
DE19756874A1 (de) | 1997-12-19 | 1999-06-24 | Basf Ag | Vorrichtung zum Herstellen von dispersen Stoffgemischen mittels Ultraschall und Verwendung einer derartigen Vorrichtung |
GB2335884A (en) | 1998-04-02 | 1999-10-06 | Cambridge Display Tech Ltd | Flexible substrates for electronic or optoelectronic devices |
US6538194B1 (en) | 1998-05-29 | 2003-03-25 | Catalysts & Chemicals Industries Co., Ltd. | Photoelectric cell and process for producing metal oxide semiconductor film for use in photoelectric cell |
US6352777B1 (en) | 1998-08-19 | 2002-03-05 | The Trustees Of Princeton University | Organic photosensitive optoelectronic devices with transparent electrodes |
US6297495B1 (en) | 1998-08-19 | 2001-10-02 | The Trustees Of Princeton University | Organic photosensitive optoelectronic devices with a top transparent electrode |
US6278055B1 (en) | 1998-08-19 | 2001-08-21 | The Trustees Of Princeton University | Stacked organic photosensitive optoelectronic devices with an electrically series configuration |
US6948843B2 (en) | 1998-10-28 | 2005-09-27 | Covaris, Inc. | Method and apparatus for acoustically controlling liquid solutions in microfluidic devices |
US6180871B1 (en) | 1999-06-29 | 2001-01-30 | Xoptix, Inc. | Transparent solar cell and method of fabrication |
US7022910B2 (en) | 2002-03-29 | 2006-04-04 | Konarka Technologies, Inc. | Photovoltaic cells utilizing mesh electrodes |
US20050268962A1 (en) | 2000-04-27 | 2005-12-08 | Russell Gaudiana | Flexible Photovoltaic cells, systems and methods |
US6509204B2 (en) | 2001-01-29 | 2003-01-21 | Xoptix, Inc. | Transparent solar cell and method of fabrication |
WO2002091483A2 (en) | 2001-05-08 | 2002-11-14 | Bp Corporation North America Inc. | Improved photovoltaic device |
US6657378B2 (en) | 2001-09-06 | 2003-12-02 | The Trustees Of Princeton University | Organic photovoltaic devices |
DE10140991C2 (de) | 2001-08-21 | 2003-08-21 | Osram Opto Semiconductors Gmbh | Organische Leuchtdiode mit Energieversorgung, Herstellungsverfahren dazu und Anwendungen |
ATE464650T1 (de) | 2001-11-22 | 2010-04-15 | Canon Kk | Lichtemissionselement, herstellungsverfahren dafür und lichtemissionsvorrichtung |
KR100844004B1 (ko) | 2002-03-15 | 2008-07-04 | 엘지디스플레이 주식회사 | 유기전계발광 소자용 투명 도전막의 제조 방법 |
US20070251570A1 (en) | 2002-03-29 | 2007-11-01 | Konarka Technologies, Inc. | Photovoltaic cells utilizing mesh electrodes |
US20070216300A1 (en) | 2002-04-04 | 2007-09-20 | International Display Systems, Inc. | Organic opto-electronic device with environmentally protective barrier |
US7825330B2 (en) | 2002-07-09 | 2010-11-02 | Fujikura Ltd. | Solar cell |
US7118692B2 (en) | 2004-10-04 | 2006-10-10 | Air Products And Chemicals, Inc. | Substituted thienothiophene monomers and conducting polymers |
US7071289B2 (en) | 2002-07-11 | 2006-07-04 | The University Of Connecticut | Polymers comprising thieno [3,4-b]thiophene and methods of making and using the same |
US7432340B2 (en) | 2002-07-11 | 2008-10-07 | Air Products And Chemicals, Inc. | Fluorinated alkyl substituted-thieno[3,4-]thiophene monomers and polymers therefrom |
AU2003287659A1 (en) | 2002-11-14 | 2004-06-15 | Sam-Shajing Sun | Photovoltaic devices based on a novel block copolymer |
DE10255964A1 (de) | 2002-11-29 | 2004-07-01 | Siemens Ag | Photovoltaisches Bauelement und Herstellungsverfahren dazu |
IL153895A (en) | 2003-01-12 | 2013-01-31 | Orion Solar Systems Ltd | Solar cell device |
EP1606846B1 (en) | 2003-03-24 | 2010-10-27 | Konarka Technologies, Inc. | Photovoltaic cell with mesh electrode |
US6936761B2 (en) | 2003-03-29 | 2005-08-30 | Nanosolar, Inc. | Transparent electrode, optoelectronic apparatus and devices |
DE10326547A1 (de) | 2003-06-12 | 2005-01-05 | Siemens Ag | Tandemsolarzelle mit einer gemeinsamen organischen Elektrode |
US20040265623A1 (en) | 2003-06-26 | 2004-12-30 | Osram Opto Semiconductors Gmbh | Conducting polymer for electronic devices |
DE602004017550D1 (de) | 2003-08-28 | 2008-12-18 | Merck Patent Gmbh | Mono-, Oligo- und Polythienoi2,3-b thiophene |
US7105237B2 (en) | 2003-10-01 | 2006-09-12 | The University Of Connecticut | Substituted thieno[3,4-B]thiophene polymers, method of making, and use thereof |
US7179543B2 (en) | 2003-10-06 | 2007-02-20 | The Trustees Of Princeton University | Doping of organic opto-electronic devices to extend reliability |
ATE452154T1 (de) * | 2003-10-15 | 2010-01-15 | Merck Patent Gmbh | Polybenzodithiophene |
EP1677316A4 (en) | 2003-10-23 | 2009-08-26 | Bridgestone Corp | TRANSPARENT CONDUCTIVE SUBSTRATE, ELECTRODE FOR COLOR-SENSITIZED SOLAR CELL AND COLOR-SENSITIZED SOLAR CELL |
US7638807B2 (en) | 2003-10-28 | 2009-12-29 | Sumitomo Metal Mining Co., Ltd. | Transparent conductive multi-layer structure, process for its manufacture and device making use of transparent conductive multi-layer structure |
US20070095391A1 (en) | 2003-11-14 | 2007-05-03 | Sam-Shajing Sun | Tandem photovoltaic devices based on a novel block copolymer |
JP2005197608A (ja) | 2004-01-09 | 2005-07-21 | Mitsubishi Heavy Ind Ltd | 光電変換装置 |
EP1555695B1 (en) | 2004-01-13 | 2011-05-04 | Sanyo Electric Co., Ltd. | Photovoltaic device |
US20050164019A1 (en) | 2004-01-22 | 2005-07-28 | General Electric Company | Charge transfer-promoting materials and electronic devices incorporating same |
JP2005206750A (ja) * | 2004-01-26 | 2005-08-04 | Konica Minolta Holdings Inc | 有機半導体材料、有機トランジスタ、電界効果トランジスタ、スイッチング素子及び5員複素環化合物 |
CN1938866A (zh) | 2004-03-31 | 2007-03-28 | 罗姆股份有限公司 | 叠层型薄膜太阳能电池及其制造方法 |
KR20070033992A (ko) | 2004-06-09 | 2007-03-27 | 메르크 파텐트 게엠베하 | 중합성 티에노[3,2-b]티오펜 |
EP1617494B1 (en) | 2004-07-02 | 2010-08-11 | Konarka Technologies, Inc. | Organic photovoltaic component with encapsulation |
US7732229B2 (en) | 2004-09-18 | 2010-06-08 | Nanosolar, Inc. | Formation of solar cells with conductive barrier layers and foil substrates |
JP4716701B2 (ja) | 2004-09-30 | 2011-07-06 | 株式会社エンプラス | 色素増感太陽電池の光電極及び色素増感太陽電池、並びに有機太陽電池の光電極 |
CN101438199A (zh) | 2004-10-25 | 2009-05-20 | 加利福尼亚大学董事会 | 有机电子器件的叠层电极 |
US20070186971A1 (en) | 2005-01-20 | 2007-08-16 | Nanosolar, Inc. | High-efficiency solar cell with insulated vias |
US20060292736A1 (en) | 2005-03-17 | 2006-12-28 | The Regents Of The University Of California | Architecture for high efficiency polymer photovoltaic cells using an optical spacer |
US20080006324A1 (en) | 2005-07-14 | 2008-01-10 | Konarka Technologies, Inc. | Tandem Photovoltaic Cells |
US20070181179A1 (en) | 2005-12-21 | 2007-08-09 | Konarka Technologies, Inc. | Tandem photovoltaic cells |
US20070267055A1 (en) | 2005-07-14 | 2007-11-22 | Konarka Technologies, Inc. | Tandem Photovoltaic Cells |
KR100696529B1 (ko) | 2005-08-02 | 2007-03-19 | 삼성에스디아이 주식회사 | 금속원소를 포함하는 광전변환소자용 전극 및 이를 채용한염료감응 태양전지 |
US7314773B2 (en) | 2005-08-17 | 2008-01-01 | The Trustees Of Princeton University | Low resistance thin film organic solar cell electrodes |
KR100658263B1 (ko) | 2005-09-29 | 2006-12-14 | 삼성전자주식회사 | 적층형 광전변환소자 및 그의 제조방법 |
KR100764362B1 (ko) | 2005-11-01 | 2007-10-08 | 삼성전자주식회사 | 태양전지용 투명 전극, 그의 제조방법 및 그를 포함하는반도체 전극 |
US8679587B2 (en) | 2005-11-29 | 2014-03-25 | State of Oregon acting by and through the State Board of Higher Education action on Behalf of Oregon State University | Solution deposition of inorganic materials and electronic devices made comprising the inorganic materials |
US20070193621A1 (en) | 2005-12-21 | 2007-08-23 | Konarka Technologies, Inc. | Photovoltaic cells |
JP5431736B2 (ja) | 2006-02-14 | 2014-03-05 | キャボット マイクロエレクトロニクス コーポレイション | インジウム錫酸化物表面をcmpする方法 |
US7863157B2 (en) | 2006-03-17 | 2011-01-04 | Silicon Genesis Corporation | Method and structure for fabricating solar cells using a layer transfer process |
US20070215879A1 (en) | 2006-03-20 | 2007-09-20 | General Electric Company | Opto-electronic devices exhibiting enhanced efficiency |
US20070295387A1 (en) | 2006-05-05 | 2007-12-27 | Nanosolar, Inc. | Solar assembly with a multi-ply barrier layer and individually encapsulated solar cells or solar cell strings |
JP2010502570A (ja) | 2006-07-26 | 2010-01-28 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング | 置換ベンゾジチオフェン類及びベンゾジセレノフェン類 |
EP2052413A2 (en) | 2006-08-08 | 2009-04-29 | Koninklijke Philips Electronics N.V. | Integrated device |
US7820782B2 (en) | 2006-10-25 | 2010-10-26 | Xerox Corporation | Poly(dithienylbenzo[1,2-b:4,5-b′]dithiophene) polymers |
US7834132B2 (en) | 2006-10-25 | 2010-11-16 | Xerox Corporation | Electronic devices |
KR100870838B1 (ko) | 2008-03-04 | 2008-11-28 | 한국철강 주식회사 | 투명전극이 코팅된 기판의 수분 제거방법 |
US20090229667A1 (en) | 2008-03-14 | 2009-09-17 | Solarmer Energy, Inc. | Translucent solar cell |
US8436134B2 (en) * | 2008-07-18 | 2013-05-07 | University Of Chicago | Semiconducting polymers |
US20100018581A1 (en) | 2008-07-24 | 2010-01-28 | Solarmer Energy, Inc. | Large area solar cell |
US20100276071A1 (en) | 2009-04-29 | 2010-11-04 | Solarmer Energy, Inc. | Tandem solar cell |
US7811161B1 (en) | 2009-05-18 | 2010-10-12 | Cnh America Llc | Corn cob collection device with stowable conveyor system having positive de-husking capability |
US8440496B2 (en) | 2009-07-08 | 2013-05-14 | Solarmer Energy, Inc. | Solar cell with conductive material embedded substrate |
US8372945B2 (en) | 2009-07-24 | 2013-02-12 | Solarmer Energy, Inc. | Conjugated polymers with carbonyl substituted thieno[3,4-B]thiophene units for polymer solar cell active layer materials |
US8399889B2 (en) | 2009-11-09 | 2013-03-19 | Solarmer Energy, Inc. | Organic light emitting diode and organic solar cell stack |
-
2008
- 2008-09-29 US US12/240,334 patent/US8367798B2/en active Active
-
2009
- 2009-09-02 EP EP09816679A patent/EP2334688A4/en not_active Withdrawn
- 2009-09-02 CN CN200980138171.8A patent/CN102164926B/zh not_active Expired - Fee Related
- 2009-09-02 BR BRPI0920822-4A patent/BRPI0920822A2/pt not_active Application Discontinuation
- 2009-09-02 WO PCT/US2009/055717 patent/WO2010036494A1/en active Application Filing
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101050221A (zh) * | 2006-04-04 | 2007-10-10 | 陈兆江 | 生产导电或发光聚合物有机配合体的噻吩衍生物及制备方法 |
EP1916250A1 (en) * | 2006-10-25 | 2008-04-30 | Xerox Corporation | Electronic devices comprising poly(dithienyl-benzodithiophenes) as semiconductors |
Non-Patent Citations (1)
Title |
---|
"Bandgap and Molecular Energy Level Control of Conjugated Polymer Photovoltaic Materials Based on Benzo[1,2-b:4,5-b′]dithiophene";Jianhui Hou,et al.;《Macromolecules》;20080723;第41卷(第16期);p6012-6018 * |
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CN102164926A (zh) | 2011-08-24 |
US20100078074A1 (en) | 2010-04-01 |
EP2334688A1 (en) | 2011-06-22 |
EP2334688A4 (en) | 2012-04-04 |
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