Departments of Chemistry, ‡Materials Science and Engineering, §Chemical and Biomolecular Engineering, and ∥Electrical and Systems Engineering, University of Pennsylvania , 231 South 34th Street, Philadelphia, Pennsylvania 19104, United States.
ACS Nano. 2014 Dec 23;8(12):12755-62. doi: 10.1021/nn505871b. Epub 2014 Dec 10.
The ability to control the molecular packing and nanoscale morphology of conjugated polymers is important for many of their applications. Here, we report the fabrication of well-ordered nanoarrays of conjugated polymers, based on the self-assembly of conjugated block copolymers at the air-liquid interface. We demonstrate that the self-assembly of poly(3-hexylthiophene)-block-poly(ethylene glycol) (P3HT-b-PEG) at the air-water interface leads to large-area free-standing films of well-aligned P3HT nanowires. Block copolymers with high P3HT contents (82-91%) formed well-ordered nanoarrays at the interface. The fluidic nature of the interface, block copolymer architecture, and rigid nature of P3HT were necessary for the formation of well-ordered nanostructures. The free-standing films formed at the interface can be readily transferred to arbitrary solid substrates. The P3HT-b-PEG films are integrated in field-effect transistors and show orders of magnitude higher charge carrier mobility than spin-cast films, demonstrating that the air-liquid interfacial self-assembly is an effective thin film fabrication tool for conjugated block copolymers.
控制共轭聚合物的分子堆积和纳米形貌对于它们的许多应用都很重要。在这里,我们报告了基于在气液界面处自组装共轭嵌段共聚物来制备共轭聚合物的有序纳米阵列。我们证明了聚(3-己基噻吩)-嵌段-聚(乙二醇)(P3HT-b-PEG)在气-水界面处的自组装导致了大区域的、高度取向的 P3HT 纳米线的自支撑薄膜。具有高 P3HT 含量(82-91%)的嵌段共聚物在界面处形成了有序的纳米阵列。界面的流体性质、嵌段共聚物结构以及 P3HT 的刚性对于形成有序的纳米结构是必要的。在界面上形成的自支撑薄膜可以很容易地转移到任意的固体基底上。P3HT-b-PEG 薄膜被集成到场效应晶体管中,并表现出比旋涂薄膜高几个数量级的载流子迁移率,这表明气-液界面自组装是一种有效的共轭嵌段共聚物的薄膜制备工具。