CN113831514A - 一种封端聚合物及其制备方法与应用 - Google Patents
一种封端聚合物及其制备方法与应用 Download PDFInfo
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- CN113831514A CN113831514A CN202111139589.XA CN202111139589A CN113831514A CN 113831514 A CN113831514 A CN 113831514A CN 202111139589 A CN202111139589 A CN 202111139589A CN 113831514 A CN113831514 A CN 113831514A
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/20—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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Abstract
Description
技术领域
本发明涉及一种封端聚合物及其制备方法与其在太阳能电池中的应用。
背景技术
近几年,聚合物太阳能电池由于其成本低、质量轻、可卷曲等优点受到学术界与工业界的高度关注。目前为止,由于聚合物给体材料和非富勒烯受体材料的不断更新,聚合物太阳能电池的效率达到了17%以上,但是相对硅基太阳能电池较低的效率制约了聚合物太阳能电池的商业发展。
通过对聚合物光伏材料主链结构的调整能够显著提高聚合物太阳能电池的效率。在富勒烯有机太阳能电池的发展时期,研究者发现在给体聚合物材料的尾部加入一个封端基能显著改善材料的性质,从而提高器件的转换效率,因而成为一种非常有效的设计有机太阳能电池新材料的策略。从2010年开始,Kim课题组用全氟丙基对P3HT材料进行封端,改善了材料在器件中的形貌,促进垂直和水平方向的相分离,提升了器件效率,随后其他的科研人员发现引入不同的功能化的封端组分进入聚合物结构中,都能对材料的性能有显著影响。但遗憾的是尽管非富勒烯太阳能电池的效率已经超过17%,封端修饰的聚合物给体材料尚未报道被应用在非富勒烯太阳能电池中。
在非富勒烯太阳能电池的发展阶段,不难发现,现有的高效聚合物给体材料绝大多数是高分子量的给体-受体型(D-A)结构构成的。其中的给D-A结构能调节分子的带隙和轨道能级,较高的分子量可以增加分子的结晶性,促进分子间的电荷传输。鉴于封端修饰对聚合物材料性能有显著影响,同时在之前的研究对聚合物封端主要集中在低分子量的聚合物,高分子量聚合物给体材料的封端研究较少。因此,设计和开发一种新型的高分子量封端聚合物给体,同时应用在非富勒烯太阳能电池中是非常重要和有意义的。
发明内容
针对现在发展的非富勒烯太阳能电池,本发明的目的是提供一种封端聚合物及其制备方法与应用,具体技术方案如下:
一种封端聚合物,所述封端聚合物的结构式如式I所示:
其中,D、π、A、E各自独立地选自未取代或含有取代基的下述基团:亚乙烯基、亚乙炔基、单环亚芳基、双环亚芳基、含至少三个环的亚芳基、单环杂亚芳基、双环杂亚芳基和含至少三个环的杂亚芳基;其中,所述双环亚芳基、含至少三个环的亚芳基、双环杂亚芳基和含至少三个环的杂亚芳基中环与环之间稠合或通过单键连接;
n代表聚合物的重复单元个数,为5-500之间的自然数。
在一些实施例中,D、π、A、E均含有1个或2个取代基,所述取代基各自独立地选自芳基、具有1-30个碳原子的烷基和具有1-30个碳原子的烷氧基。
在一些实施例中,D选自未取代或含有取代基的下述基团:
其中,R1选自氢、具有1-30个碳原子的烷基、具有1-30个碳原子的烷氧基、氰基、硝基、酯基、芳基、芳烷基、卤素、卤代烷基、杂烷基、烯基以及单键、双键、三键或其组合的取代基取代的芳基。
在一些实施例中,π选自未取代或含有取代基的下述基团:
其中,R2选自氢、具有1-30个碳原子的烷基、具有1-30个碳原子的烷氧基、氰基、硝基、酯基、芳基、芳烷基、卤素、卤代烷基、杂烷基、烯基以及单键、双键、三键或其组合的取代基取代的芳基。
在一些实施例中,A选自未取代或含有取代基的下述基团:
其中,R3选自氢、具有1-20个碳原子的烷基、具有1-20个碳原子的烷氧基。
在一些实施例中,E选自未取代或含有取代基的下述基团:
其中,R4选自氢、具有1-20个碳原子的烷基、具有1-20个碳原子的烷氧基。
在一些实施例中,所述封端聚合物的数均分子量为1000至1000000,优选的数均分子量为3000至500000,进一步优选的数均分子量为20000至200000。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。
一种所述封端聚合物的制备方法,采用式II所示的化合物和式III所示的化合物在催化剂的作用下发生偶联反应,得到式Ⅰ所述封端聚合物;
Y-E (III)
其中,D、π、A和E的定义同式I;
式II中的X选自I、Br或Cl,式III中的Y选自硼酸基团、硼酸酯基团、卤化锌基团或三烷基锡基团;或者
式III中的Y选自I、Br或Cl,且式II中的X选自硼酸基团、硼酸酯基团、卤化锌基团或三烷基锡基团;
在一些实施例中,所述硼酸基团选自1,3,2-二氧杂硼烷-2-基、4,4,5,5-四甲基-1,2,3-二氧杂环戊硼烷-2-基或5,5-二甲基-1,3,2-二氧杂硼烷-2-基;所述卤化镁基团选自氯化镁、溴化镁或碘化镁;所述卤化锌基团为氯化锌或溴化锌;所述三烷基锡基团选自三甲基锡、三乙基锡或三丁基锡;所述催化剂选自[1,3-双(二苯基膦基)丙烷]二氯镍(Ⅱ)、[1,2-双(二苯基膦基)乙烷]二氯镍(Ⅱ)、四(三苯基膦)钯(0)、双(二亚苄基丙酮)钯(0)、氯化钯或醋酸钯。
一种半导体组合物,由所述封端聚合物和掺加剂组成,两者可按照任意比例混合,如封端聚合物与掺加剂的质量比1:1.2等。
所述掺加剂使得当包括光或电压的激发源施加至该组合时,在掺加剂和封端聚合物之间发生电荷转移和/或能量转移;所述掺加剂为富勒烯或其衍生物;优选的所述掺加剂为[6,6]-苯基C61丁酸甲酯、[6,6]-苯基C71丁酸甲酯、含茚富勒烯或含茚多稠环非富勒烯材料。
所述封端聚合物还可用作如光检测器器件、太阳能电池器件等光伏器件中的光伏材料。例如,所述封端聚合物或半导体组合物在制备聚合物太阳能电池器件中的应用,所述聚合物太阳能电池器件包含本体异质结结构。
一种光电器件,包括第一电极、与所述第一电极间隔开的第二电极、以及在所述第一电极和第二电极之间设置的至少一层活性材料层,所述活性材料层中含有所述封端聚合物。
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、试剂或者反应条件,而是可以变化。本发明所用的术语“烷基”指支化的或未支化的饱和烷基,其通常但并非必需地含有1至30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”(即除了碳原子之外的原子,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卤素、羟基、烷基硫代、烷氧基、芳氧基、烷基羰基、酰氧基、硝基、腈基等的官能团。
相比于现有技术,本发明具有如下有益效果:
本发明通过对聚合物的端基进行修饰,显著提升了聚合物给体材料与受体材料的共混性,促进分子间的电荷转移,从而提升材料的器件性能;同时封端的操作方法较为简单,没有严苛的聚合条件,同时能够达到不错的封端效果;封端基材料的用量较少,少量封端基就能显著提升材料的器件性能,实现对成熟材料的性能修补。
附图说明
图1为实施例1制备未封端聚合物PM6的化学反应示意图。
图2为实施例1制备封端单元M1的化学反应示意图。
图3为实施例1制备封端聚合物PM6TPO的化学反应示意图。
图4为实施例1制备封端聚合物PM6TPO的吸收光谱图。
图5为实施例1制备封端聚合物PM6TPO的循环伏安特性曲线图。
图6为实施例1制备聚合物太阳能电池器件的J-V曲线。
图7为实施例2制备封端单元M2的化学反应示意图。
图8为实施例2制备封端聚合物PM6TPN的化学反应示意图。
图9为实施例3制备未封端聚合物PBDB-T的化学反应示意图。
图10为实施例3制备封端聚合物PBDB-TT的化学反应示意图。
具体实施方式
在描述本发明的实施方案时,为了清楚起见,使用了特定的术语。然而,本发明无意局限于所选择的特定术语。应了解每个特定元件包括类似的方法运行以实现类似目的的所有技术等同物。
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。所有溶剂都是以HPLC级购得,并且所有反应在氩气惰性气氛下进行。除非另外指出,否则所有试剂都是商业获得的。
实施例1
(1)未封端PM6聚合物的合成
取单体(4,8-双(5-(2-乙基己基)-4-氟噻吩-2-基)苯并[1,2-b:4,5-b']二噻吩-2,6-二基)双(三甲基锡烷)(0.0941g,0.1mmol)和1,3-双(5-溴噻吩-2-基)-5,7-双(2-乙基己基)-4H,8H-苯并[1,2-c:4,5-c']二噻吩-4,8-二酮(0.0767g,0.1mmol),将其溶入甲苯(10mL)后,用氩气排空气5分钟,再加入催化剂四(三苯基膦)钯(0)(10mg)后继续排空气25分钟。然后在甲苯回流温度下聚合16小时候停止。将聚合物溶液冷却至室温,慢慢倾倒入甲醇(50mL)中,沉析出的固体聚合物在索氏提取器内依次用甲醇、正己烷来洗脱。最后用三氯甲烷溶解后沉析到甲醇中,过滤,真空干燥1天得到黑色固体粉末的未封端聚合物PM6。其化学反应示意图如图1所示。
(2)封端单元(5-(4-甲氧基苯基)噻吩2-基)三甲基锡烷的合成
将1-溴-4-甲氧基苯(0.5g,2.67mmol)和2-(三-N-丁基甲锡烷基)噻吩(2.69g,6.68mmol)加入50mL烧瓶中并溶解在20mL的甲苯中,用氮气鼓气10分钟。将四三苯基膦钯(15mg)加入烧瓶后,再鼓气10分钟。将反应液逐渐加热至110℃并在110℃和氮气氛围下反应24小时。反应完毕后,冷却至室温,倒入水中,用二氯甲烷萃取,收集有机相,水洗数次,无水硫酸镁干燥,旋干有机相,粗产物过硅胶柱(CH2Cl2/PE=1/5淋洗),得黄色固体产物化合物,即为2-(4-甲氧基苯基)噻吩(0.38g,75%收率)。
将2-(4-甲氧基苯基)噻吩(0.3g,1.58mmol)加入到50mL烧瓶中并溶解在20mL四氢呋喃中。鼓气15分钟后,在-78℃下将正丁基锂(2.4M,1.97mL)缓慢加入到反应液中,在-78℃下反应2小时。然后在-78℃下一次性加入三甲基氯化锡(1M,5.53mL),缓慢恢复室温后反应过夜。反应终止后向混合液中加入10mL水,用乙醚萃取混合物三次并用无水硫酸镁干燥。将旋干溶剂后,用乙醇重结晶,得到蓝色片状固体,即为(5-(4-甲氧基苯基)噻吩2-基)三甲基锡烷(0.45g,收率80%)。
上述化学反应的示意图如图2所示。
(3)封端聚合物PM6TPO的合成
将PM6(50mg)、5-(4-甲氧基苯基)噻吩2-基)三甲基锡烷(60mg,0.17mmol)和四三苯基膦钯(10mg)加入50mL烧瓶中并溶解在20mL的甲苯中,再加入2mL的无水N,N-二甲基甲酰胺溶液,用氮气鼓气10分钟。将反应液逐渐加热至110℃并在110℃和氮气氛围下反应24小时。反应结束后,停止加热并冷却至室温,将混合物沉降到60mL甲醇中并过滤。将粗产物进行索氏提取器,提取液用甲醇和正己烷提取后,将粗产物取出,再通过硅胶柱提纯,得到产物(65%收率)。其化学反应示意图如图3所示。
(4)封端聚合物的可加工性和利用吸收光谱的光学带隙的测量
将步骤(3)中制得的封端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。发现聚合物PM6TPO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PM6TPO的氯仿溶液旋涂至玻璃片上而制得高品质薄膜。
步骤(3)中制备的封端聚合物在氯仿溶液和膜状态下测得的吸收光谱如图4所示。聚合物的光学带隙使用经验公式为Eg=1240/λ吸收起始,其中:Eg为聚合物的光学带隙;λ吸收起始为吸收光谱在长波方向的起点。计算结果示于表1中。
表1.封端聚合物的光学吸收数据
聚合物PM6TPO在溶液中的最大吸收位置为582nm,吸收起始位置为672nm。当聚合物PM6TPO旋涂成膜后,它的最大吸收和起始吸收都分别红移至583nm和683nm。说明聚合物1在成膜后分子链间的聚集态加强。从聚合物膜起始吸收的位置,根据公式Eg opt=1240/λ吸收起始,膜(eV),得到聚合物PM6TPO的光学带隙为1.81eV。
(5)利用电化学循环伏安法的分子轨道能级测量
根据李永舫(Synth.Met.1999,99,243)的方法测定聚合物的分子轨道能级。将步骤(3)中制得的封端聚合物(1.0mg)溶解于1mL氯仿中,然后滴加该溶液至工作电极如铂片上;使用0.1mol/L Bu4NPF6的乙腈溶液作为电解质;以铂丝作为对电极;银丝作为参比电极。使用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、LUMO能级。封端聚合物的循环伏安数据如图5所示。封端聚合物的HOMO、LUMO能级分别为-5.51eV和-3.62eV。
(6)制备聚合物太阳能电池器件
器件结构为ITO/PEDOT:PSS/聚合物:Y6/PDINN/Ag。依次用肥皂水、去离子水、丙酮和异丙醇超声清洗ITO玻璃基底,在110℃下真空干燥过夜后用臭氧处理20分钟。然后在清洗干净的ITO玻璃基底上将PEDOT:PSS以4000rpm旋涂20秒并在200℃下退火30分钟。将具有不同浓度添加剂和给受体重量比PM6TPO和Y6的混合物溶解在氯仿(CF)中,然后活性层以3000rpm旋涂30秒。待干后旋涂PDINN电子传输层和镀Ag电极层。制得的太阳能电池器件由Keithley 2400在AM1.5G的模拟光下测得的光电转换效率为15.88%,开路电压Voc为0.87eV,短路电流密度Jsc=25.18mAcm-2,填充因子FF=0.727。同时,随着活性层膜厚增加至600nm,能量转化效率以然可以维持为10.85%。其中,太阳光模拟器是通过校准的硅太阳能电池来校正。电流密度-电压(J-V)曲线如图6所示。
实施例2
(1)未封端PM6聚合物的合成
取单体(4,8-双(5-(2-乙基己基)-4-氟噻吩-2-基)苯并[1,2-b:4,5-b']二噻吩-2,6-二基)双(三甲基锡烷)(0.0941g,0.1mmol)和1,3-双(5-溴噻吩-2-基)-5,7-双(2-乙基己基)-4H,8H-苯并[1,2-c:4,5-c']二噻吩-4,8-二酮(0.0767g,0.1mmol),将其溶入甲苯(10mL)后,用氩气排空气5分钟,再加入催化剂四(三苯基膦)钯(0)(10mg)后继续排空气25分钟。然后在甲苯回流温度下聚合16小时候停止。将聚合物溶液冷却至室温,慢慢倾倒入甲醇(50mL)中,沉析出的固体聚合物在索氏提取器内依次用甲醇、正己烷来洗脱。最后用三氯甲烷溶解后沉析到甲醇中,过滤,真空干燥1天得到黑色固体粉末的未封端聚合物PM6。其化学反应示意图如图1所示。
(2)封端单元(4-(5-(三甲基甲锡烷基)噻吩2-基)苄腈的合成
将4-溴苄腈(0.5g,2.75mmol)和2-(三-N-丁基甲锡烷基)噻吩(2.69g,6.68mmol)加入50mL烧瓶中并溶解在20mL的甲苯中,用氮气鼓气10分钟。将四三苯基膦钯(15mg)加入烧瓶后,再鼓气10分钟。将反应液逐渐加热至110℃并在110℃和氮气氛围下反应24小时。反应完毕后,冷却至室温,倒入水中,用二氯甲烷萃取,收集有机相,水洗数次,无水硫酸镁干燥,旋干有机相,粗产物过硅胶柱(CH2Cl2/PE=1/5淋洗),得黄色固体产物化合物,即为4-(噻吩-2-基)苄腈(0.38g,75%收率)。
将4-(噻吩-2-基)苄腈(0.3g,1.62mmol)加入到50mL烧瓶中并溶解在20mL四氢呋喃中。鼓气15分钟后,在-78℃下将正丁基锂(2.4M,1.97mL)缓慢加入到反应液中,在-78℃下反应2小时。然后在-78℃下一次性加入三甲基氯化锡(1M,5.53mL),缓慢恢复室温后反应过夜。反应终止后向混合液中加入10mL水,用乙醚萃取混合物三次并用无水硫酸镁干燥。将旋干溶剂后,用乙醇重结晶,得到黄色粉状固体,即为(4-(5-(三甲基甲锡烷基)噻吩2-基)苄腈(0.45g,收率80%)。
上述化学反应的示意图如图7所示。
(3)封端聚合物PM6TPN的合成
将PM6(50mg)、(4-(5-(三甲基甲锡烷基)噻吩2-基)苄腈(60mg,0.17mmol)和四三苯基膦钯(10mg)加入50mL烧瓶中并溶解在20mL的甲苯中,再加入2mL的无水N,N-二甲基甲酰胺溶液,用氮气鼓气10分钟。将反应液逐渐加热至110℃并在110℃和氮气氛围下反应24小时。反应结束后,停止加热并冷却至室温,将混合物沉降到60mL甲醇中并过滤。将粗产物进行索氏提取器,提取液用甲醇和正己烷提取后,将粗产物取出,再通过硅胶柱提纯,得到产物(65%收率)。其化学反应示意图如图8所示。
实施例3
(1)未封端PBDB-T聚合物的合成
取单体(4,8-双(5-(2-乙基己基)-噻吩-2-基)苯并[1,2-b:4,5-b']二噻吩-2,6-二基)双(三甲基锡烷)(0.0904g,0.1mmol)和1,3-双(5-溴噻吩-2-基)-5,7-双(2-乙基己基)-4H,8H-苯并[1,2-c:4,5-c']二噻吩-4,8-二酮(0.0767g,0.1mmol),将其溶入甲苯(10mL)后,用氩气排空气5分钟,再加入催化剂四(三苯基膦)钯(0)(10mg)后继续排空气25分钟。然后在甲苯回流温度下聚合16小时候停止。将聚合物溶液冷却至室温,慢慢倾倒入甲醇(50mL)中,沉析出的固体聚合物在索氏提取器内依次用甲醇、正己烷来洗脱。最后用三氯甲烷溶解后沉析到甲醇中,过滤,真空干燥1天得到黑色固体粉末的未封端聚合物PM6。其化学反应示意图如图9所示。
(2)封端聚合物PBDB-TT的合成
将PBDB-T(50mg)、三丁基(2-噻吩基)锡(63mg,0.17mmol)和四三苯基膦钯(10mg)加入50mL烧瓶中并溶解在20mL的甲苯中,再加入2mL的无水N,N-二甲基甲酰胺溶液,用氮气鼓气10分钟。将反应液逐渐加热至110℃并在110℃和氮气氛围下反应24小时。反应结束后,停止加热并冷却至室温,将混合物沉降到60mL甲醇中并过滤。将粗产物进行索氏提取器,提取液用甲醇和正己烷提取后,将粗产物取出,再通过硅胶柱提纯,得到产物(65%收率)。其化学反应示意图如图10所示。
尽管为了说明的目的,已描述了本发明的示例性实施方式,但是本领域的技术人员将理解,不脱离所附权利要求中公开的发明的范围和精神的情况下,可以在形式和细节上进行各种修改、添加和替换等的改变,而所有这些改变都应属于本发明所附权利要求的保护范围,并且本发明要求保护的产品各个部门和方法中的各个步骤,可以以任意组合的形式组合在一起。因此,对本发明中所公开的实施方式的描述并非为了限制本发明的范围,而是用于描述本发明。相应地,本发明的范围不受以上实施方式的限制,而是由权利要求或其等同物进行限定。
Claims (10)
2.根据权利要求1所述的封端聚合物,其特征在于,D、π、A、E均含有1个或2个取代基,所述取代基各自独立地选自芳基、具有1-30个碳原子的烷基和具有1-30个碳原子的烷氧基;所述封端聚合物的数均分子量为1000至1000000,优选的数均分子量为3000至500000,进一步优选的数均分子量为20000至200000。
7.一种权利要求1-6任一项所述封端聚合物的制备方法,其特征在于,采用式II所示的化合物和式III所示的化合物在催化剂的作用下发生偶联反应,得到式Ⅰ所述封端聚合物;
Y-E (III)
其中,D、π、A和E的定义同式I;
式II中的X选自I、Br或Cl,式III中的Y选自硼酸基团、硼酸酯基团、卤化锌基团或三烷基锡基团;或者
式III中的Y选自I、Br或Cl,且式II中的X选自硼酸基团、硼酸酯基团、卤化锌基团或三烷基锡基团;
优选的,所述硼酸基团选自1,3,2-二氧杂硼烷-2-基、4,4,5,5-四甲基-1,2,3-二氧杂环戊硼烷-2-基或5,5-二甲基-1,3,2-二氧杂硼烷-2-基;所述卤化镁基团选自氯化镁、溴化镁或碘化镁;所述卤化锌基团为氯化锌或溴化锌;所述三烷基锡基团选自三甲基锡、三乙基锡或三丁基锡;所述催化剂选自[1,3-双(二苯基膦基)丙烷]二氯镍(Ⅱ)、[1,2-双(二苯基膦基)乙烷]二氯镍(Ⅱ)、四(三苯基膦)钯(0)、双(二亚苄基丙酮)钯(0)、氯化钯或醋酸钯。
8.一种半导体组合物,其特征在于,由权利要求1-6中任一项所述的封端聚合物和掺加剂组成;
所述掺加剂为富勒烯或其衍生物;优选的所述掺加剂为[6,6]-苯基C61丁酸甲酯、[6,6]-苯基C71丁酸甲酯、含茚富勒烯或含茚多稠环非富勒烯材料。
9.权利要求1-6中任一项所述封端聚合物或权利要求8所述半导体组合物在制备聚合物太阳能电池器件中的应用,其特征在于,所述聚合物太阳能电池器件包含本体异质结结构。
10.一种光电器件,包括第一电极、与所述第一电极间隔开的第二电极、以及在所述第一电极和第二电极之间设置的至少一层活性材料层,其特征在于,所述活性材料层中含有权利要求1-6中任一项所述的封端聚合物。
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