Osaka Itaru, Zhang Rui, Sauvé Geneviève, Smilgies Detlef-M, Kowalewski Tomasz, McCullough Richard D
Department of Chemistry, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213, USA.
J Am Chem Soc. 2009 Feb 25;131(7):2521-9. doi: 10.1021/ja801475h.
Owing to their superior transport properties, poly(alkylthiophenes) and their derivatives emerged as one of the most widely studied semiconducting polymers with potential applications in organic electronics. It is now generally acknowledged that one of the particularly effective ways to increase the carrier mobility in these materials is by increasing the length of the conjugated backbones. Some recent reports suggest also that carrier mobilities can be further enhanced by highly crystalline arrangement (and interdigitation) of alkyl side chains possibly because it promotes the formation of extensive layered structures favorable for carrier transport. Results presented here demonstrate that, surprisingly, none of these factors are actually necessary for good electronic performance of polythiophene-like systems. Thiophene-based semiconducting polymers bearing thiazolothiazole unit (PTzQT) described here were shown to have very high carrier mobilities (approximately 0.3 cm(2)/Vs) despite their low molecular weight and uneven spacing of alkyl side chains, which suppressed high side chain crystallinity/interdigitation as revealed by thermal analysis and X-ray scattering. The highly disordered nature of these materials extended to the nanoscale level as evident from atomic force microscopy images, which have shown only the presence of small domains packed into isotropic amorphous-like superstructures with lateral correlation lengths increasing with the length of alkyl side chains. The observed concomitant increase of carrier mobilities points to the possible role of characteristic length of surface roughness as the key parameter controlling carrier transport in disordered, noninterdigitating systems.
由于其优异的传输性能,聚(烷基噻吩)及其衍生物成为研究最为广泛的半导体聚合物之一,在有机电子学领域具有潜在应用。目前普遍认为,提高这些材料中载流子迁移率的一种特别有效的方法是增加共轭主链的长度。最近的一些报道还表明,通过烷基侧链的高度结晶排列(和相互交错)可以进一步提高载流子迁移率,这可能是因为它促进了有利于载流子传输的广泛层状结构的形成。此处给出的结果表明,令人惊讶的是,对于聚噻吩类体系的良好电子性能而言,这些因素实际上都不是必需的。本文所述的带有噻唑并噻唑单元的基于噻吩的半导体聚合物(PTzQT),尽管其分子量较低且烷基侧链间距不均匀(热分析和X射线散射表明这抑制了高侧链结晶度/相互交错),但仍显示出非常高的载流子迁移率(约0.3 cm²/Vs)。这些材料的高度无序性质延伸到了纳米尺度,原子力显微镜图像表明,只存在小区域堆积成各向同性的类非晶超结构,其横向相关长度随烷基侧链长度增加。观察到的载流子迁移率的相应增加表明,表面粗糙度特征长度可能作为控制无序、非相互交错体系中载流子传输的关键参数发挥作用。