Very Large Silacylic Substituent Effects on Response in Silole-Based Polymer Transistors
Very Large Silacylic Substituent Effects on Response in Silole-Based Polymer Transistors
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DOI：
10.1021/cm200009k
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发表时间：
2011-04-26
影响因子：
8.6
通讯作者：
Marks, Tobin
中科院分区：
文献类型：
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作者：
Huang, Hui;Youn, Jangdae;Marks, Tobin
了解分子结构和有机薄膜晶体管性能之间的相互关系是实现新型有机半导体实现优异器件特性的关键。在这里，我们报道了基于二硫代硅烷的齐聚物和具有硅环烷基取代基的共聚物的合成、表征和在有机场效应晶体管(OFET)中的电荷传输特性。烷基在硅原子上的硅环化反应减少了空间位阻，缩短了固态分子间的pi-pi接触，提高了低聚物的电荷传输能力。低聚物3，3‘-二己基硅烯-2，2’：5，2“：5”，2“”：1：5“”：2“”：5“”，2“，2”-六茂铁(SM5)不具有FET活性，而3，3‘-环戊基硅烯-2，2’：5，2“：5，2‘：5，2”：3，3’-环丁基硅烯(SM4)和3，3“-环丁基硅烯-2，2”：5“，2”：5“，2”“，2”“：5”，“2‘-六硫吩场效应晶体管(SM3)分别为2.6x10(-4)和3.4x10(-4)cm(2)/(V S)。单晶结构数据和熔点派生的分子间堆积趋势与这些FET结果相似。基于相同二硫代硅醇环烯丙基的共聚物P1-P4的空穴迁移率分别为2×10(-5)、6×10(-4)、3×10(-4)和2×10(-3)cm(2)/V.s，比含硅烷基长取代基的类似聚合物的空穴迁移率低2×10(-5)、6×10(-4)、3×10(-4)和2×10(-3)cm(2)/V.s，这意味着硅烷基取代基的增溶和自组装功能对于优化迁移率是重要的。有趣的是，共聚物[Poly{[N，N‘-bis(2-octyl-dodecy1)-1，4，5，8-naphthalenedicarbaximide-2，6-diyl]-alt-5，5’-(3，3‘-cyclopentanylsilylene-2，2’-bithiophene(135)]薄膜有序程度最高，热处理后的电子迁移率为4×10(-3)cm(2)/V.s。所有这些OFET都表现出良好的环境稳定性，这归因于它们的低位HOMO(>；比P3HT低0.2 eV)，这是在聚噻吩骨架中引入竖井状核心的结果。
Understanding the interrelationships between molecular structure and organic thin film transistor performance is key to the realization of novel organic semiconductors achieving superior device characteristics. Herein we report the synthesis, characterization, and charge-transporting properties in organic field-effect transistors (OFETs) of dithieno silole-based oligomers and copolymers having silacycloalkyl substituents. Silacyclization of the alkyl substituents on the silole silicon atom reduces steric encumbrance, contracts solid state intermolecular pi-pi contacts, and enhances the charge-transport capacity of the oligomers. Oligomer 3,3'-dihexylsilylene-2,2':5,2 '':5',2 ''':1: 5 '',2 '''':5 ''',2 ''''''-sexithiophene (SM5) with two Si-n-hexyl substituents is not FET-active, while.:he mobilities of 3,3'-cyclopentanylsilylene-2,2':5,2 '':5',2 '': -sexithiophene (SM4) and 3,3'-cyclobutysilylene-2,2':5,2 '': 5',2 '':5 '',2 '''':5 ''',2 ''''-sexithiophene (SM3) FETs are 2.6 x 10(-4) and 3.4 x 10(-4) cm(2)/(V s), respectively. Single crystal structural data and melting point derived intermolecular packing trends parallel these FET results. Copolymers P1-P4 based on the same dithienosilole cycloallcyl cores exhibit optimized hole mobilities of 2 x 10(-5), 6 x 10(-4), 3 x 10(-4), and 2 x 10(-3) cm(2)/V.s, respectively, lower than that of analogous silole-containing polymers with long Si-alkyl substituents, implying that the solubilizing and self-assembly functions of Sialkyl substituents are important for optimizing the mobility. Interestingly, copolymer [poly{[N,N'-bis(2-octyl-dodecy1)-1,4,5,8-naphthalenedicarbaximide-2,6-diyl]-alt-5,5'-(3,3'-cyclopentanylsilylene-2,2'-bithiophene (135) films are the most ordered and exhibit a good electron mobility of 4 x 10(-3) cm(2)/V.s after thermal annealing. All of these OFETs exhibit good ambient-stability, which is attributed to their low-lying HOMOs (>0.2 eV lower than that of P3HT), a consequence of introducing silole cores into polythiophene backbones.