Controlling Crystal Orientation in Films of Conjugated Polymers by Tuning the Surface Energy

IF 5.1 1区化学 Q1 POLYMER SCIENCE

Macromolecules Pub Date : 2024-10-29 DOI:10.1021/acs.macromol.4c01819

Oleksandr Dolynchuk, Robert T. Kahl, Florian Meichsner, Alexander J. Much, Andrii Pechevystyi, Anna Averkova, Andreas Erhardt, Mukundan Thelakkat, Thomas Thurn-Albrecht

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Abstract

It has been a long-term goal to understand the molecular orientation in films of conjugated polymers, which is crucial to their efficient exploitation. Here, we show that the surface energies determine the crystal orientation in films of model conjugated polymers, substituted polythiophenes crystallized on substrates. We systematically increase the surface energy of edge-on crystals formed at the vacuum interface by attaching polar groups to the ends of the polymer side chains. This suppresses crystallization at the vacuum interface, resulting in a uniform face-on crystal orientation induced by the graphene substrate in polythiophene films as thick as 200 nm, which is relevant for devices. Surprisingly, face-on crystal orientation is attained in the modified polythiophenes crystallized even on amorphous surfaces. Furthermore, for the samples with still competing interfacial interactions, the crystal orientation can be switched in the same sample, depending on the crystallization conditions. Thus, we report a fundamental understanding and control of the equilibrium crystal orientation in films of conjugated polymers.

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通过调节表面能控制共轭聚合物薄膜的晶体取向

了解共轭聚合物薄膜中的分子取向一直是我们的长期目标，这对其有效利用至关重要。在这里，我们证明了表面能决定了模型共轭聚合物薄膜的晶体取向，即在基底上结晶的取代聚噻吩。我们通过在聚合物侧链末端附加极性基团，系统地增加了在真空界面上形成的边缘晶体的表面能。这抑制了真空界面处的结晶，从而在厚度达 200 nm 的聚噻吩薄膜中形成了由石墨烯基底诱导的均匀的面朝上晶体取向，这与设备息息相关。令人惊讶的是，即使在无定形表面结晶的改性聚噻吩也能获得面朝上的晶体取向。此外，对于仍存在竞争性界面相互作用的样品，晶体取向可根据结晶条件在同一样品中切换。因此，我们报告了对共轭聚合物薄膜中平衡晶体取向的基本理解和控制。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Macromolecules 工程技术-高分子科学

CiteScore

9.30

自引率

16.40%

发文量

942

审稿时长

2 months

期刊介绍： Macromolecules publishes original, fundamental, and impactful research on all aspects of polymer science. Topics of interest include synthesis (e.g., controlled polymerizations, polymerization catalysis, post polymerization modification, new monomer structures and polymer architectures, and polymerization mechanisms/kinetics analysis); phase behavior, thermodynamics, dynamic, and ordering/disordering phenomena (e.g., self-assembly, gelation, crystallization, solution/melt/solid-state characteristics); structure and properties (e.g., mechanical and rheological properties, surface/interfacial characteristics, electronic and transport properties); new state of the art characterization (e.g., spectroscopy, scattering, microscopy, rheology), simulation (e.g., Monte Carlo, molecular dynamics, multi-scale/coarse-grained modeling), and theoretical methods. Renewable/sustainable polymers, polymer networks, responsive polymers, electro-, magneto- and opto-active macromolecules, inorganic polymers, charge-transporting polymers (ion-containing, semiconducting, and conducting), nanostructured polymers, and polymer composites are also of interest. Typical papers published in Macromolecules showcase important and innovative concepts, experimental methods/observations, and theoretical/computational approaches that demonstrate a fundamental advance in the understanding of polymers.