Max Planck Institute for Polymer Research, Mainz, Germany.
J Am Chem Soc. 2011 Mar 2;133(8):2605-12. doi: 10.1021/ja108861q. Epub 2011 Feb 3.
In this article, the design paradigm involving molecular weight, alkyl substituents, and donor-acceptor interaction for the poly[2,6-(4,4-bis-alkyl-4H-cyclopenta[2,1-b;3,4-b']-dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)] (cyclopentadithiophene-benzothiadiazole) donor-acceptor copolymer (CDT-BTZ) toward field-effect transistors (FETs) with ultrahigh mobilities is presented and discussed. It is shown that the molecular weight plays a key role in improving hole mobilities, reaching an exceptionally high value of up to 3.3 cm(2) V(-1) s(-1). Possible explanations for this observation is highlighted in conjunction with thin film morphology and crystallinity. Hereby, it is found that the former does not change, whereas, at the same time, crystallinity improved with ever growing molecular weight. Furthermore, other important structural design factors such as alkyl chain substituents and donor-acceptor interaction between the polymer backbones potentially govern intermolecular stacking distances crucial for charge transport and hence for device performance. In this aspect, for the first time we attempt to shed light onto donor-acceptor interactions between neighboring polymer chains with the help of solid state nuclear magnetic resonance (NMR). On the basis of our results, polymer design principles are inferred that might be of relevance for prospective semiconductors exhibiting hole mobilities even exceeding 3 cm(2) V(-1) s(-1).
本文提出并讨论了一种涉及分子量、烷基取代基和供体-受体相互作用的设计范例,用于设计具有超高迁移率的场效应晶体管(FET)的聚[2,6-(4,4-双烷基-4H-环戊二噻吩)-交替-4,7-(2,1,3-苯并噻二唑)](环戊二噻吩-苯并噻二唑)给体-受体共聚物(CDT-BTZ)。结果表明,分子量在提高空穴迁移率方面起着关键作用,达到了高达 3.3 cm(2) V(-1) s(-1)的异常高值。结合薄膜形貌和结晶度,对此观察结果进行了重点说明。由此发现,前者没有变化,而同时结晶度随着分子量的不断增加而提高。此外,其他重要的结构设计因素,如聚合物主链上的烷基链取代基和供体-受体相互作用,可能会影响分子间堆积距离,这对电荷输运以及器件性能至关重要。在这方面,我们首次尝试借助固态核磁共振(NMR)来阐明相邻聚合物链之间的供体-受体相互作用。基于我们的结果,推断出了聚合物设计原则,这对于表现出甚至超过 3 cm(2) V(-1) s(-1)的空穴迁移率的潜在半导体可能具有重要意义。