Search

It remains challenging to comprehensively understand the packing models of conjugated polymers, in which side chains play extremely critical roles. The side chains are typically flexible and non‐conductive and are widely used to improve the polymer solubility in organic solutions. Herein, a buffer chain model is proposed to describe link between conjugated backbone and side chains for understanding the relationship of crystallization competition of conductive conjugated backbones and non‐conductive side chains. A longer buffer chain is beneficial for alleviating such crystallization competition and further promoting the spontaneous packing of conjugated backbones, resulting in enhanced charge transport properties. Our results provide a novel concept for designing conjugated polymers towards ordered organization and enhanced electronic properties and highlight the importance of balancing the competitive interactions between different parts of conjugated polymers. [ABSTRACT FROM AUTHOR]

Strong interchain interactions of conjugated polymers usually result in poor miscibility with molecular dopants, limiting the doping efficiency because of uncontrolled phase separation. We have developed a strategy to achieve efficient charge‐transport and high doping miscibility in n‐doped conjugated polymers. We solve the miscibility issue through disorder side‐chains containing dopants better. Systemic structural characterization reveals a farther side‐chain branching point will lead to higher disorders, which provides appropriate sites to accommodate extrinsic molecular dopants without harming original chain packings and charge‐transport channels. Therefore, better sustainability of solid‐state microstructure is obtained, yielding a stable conductivity even when overloading massive dopants. This work highlights the importance of realizing high host‐dopant miscibility in molecular doping of conjugated polymers. [ABSTRACT FROM AUTHOR]

The role of solution aggregates on the charge transport process of conjugated polymers in electronic devices has gained increasing attention; however, the correlation of the charge carrier mobilities between the solution aggregates and the solid‐state films remains elusive. Herein, three polymers, FBDOPV‐2T, FBDOPV‐2F2T, and FBDOPV‐4F2T, are designed and synthesized with distinct aggregation behavior in solution. By combining contact‐free ultrafast terahertz (THz) spectroscopy and field‐effect transistor measurements, we track the charge carrier mobility of the aggregates of these polymers from the solution to the thin‐film state. Remarkably, the mobility of these three polymers is found to follow nearly the same trend (FBDOPV‐2T>FBDOPV‐2F2T≫FBDOPV‐4F2T) in both solutions and thin‐film states. The quantitative mobility correlation indicates that the charge transport properties of solution aggregates play a critical role in determining the thin‐film charge transport properties and final device performance. Our results highlight the importance of investigating and controlling solution aggregation structures towards efficient organic electronic devices. [ABSTRACT FROM AUTHOR]

Crystal structure of conjugated molecules and polymers is fundamentally critical to understand their multilevel microstructures, carrier transport, and diverse functions. However, to determine the crystal structure of conjugated polymers is a significant challenge, mainly due to the poor crystallinity, weak diffraction, and instability under high‐energy radiation. Here, we build the possible crystal structures of eight typical conjugated polymers, covering several widely used molecular segments in organic optoelectronics. We model the packing structures of these seed polymers based on synchrotron X‐ray diffractions and molecular simulations. These crystal structures provide a new platform to predict the packing structures of more related polymer systems, extending the molecular scope. Based on this polymer crystal structure database, the multiscale microstructures and charge transport properties of conjugated polymers can be predicted before experiments. This study sets up a polymer crystal structure database to eliminate the current trial‐and‐error approaches and accelerating the design of high‐performance conjugated polymers. [ABSTRACT FROM AUTHOR]

The macroscopic functions and properties of conjugated polymers depend on their microcosmic morphology and microstructure in the solid state. However, such morphology and microstructure from molecules to solid states are complicated. Therefore, it is a significant challenge to reveal the relationship among molecular structures to the complex microstructure and finally to device functions. This review focuses on the formation, behavior, and evolution of solution-state aggregation of conjugated polymers, which can influence and even determine the solid-state morphology and microstructure, ultimately clarifying the relationship between the microstructure and the properties of conjugated polymers. The critical role of solution-state aggregation is highlighted from a theoretical understanding of molecular interactions between polymer chains (conjugated backbones and/or flexible side chains) and solvent molecules. We highlight the recent progress on high-performance polymer-based devices through the solution-state aggregation strategy. Furthermore, we summarize the challenges and essential research direction on the solution-state aggregation, which will be addressed and established in the future. Therefore, an in-depth understanding of polymer aggregation will advance the development of high-performance conjugated polymers in various functional devices. [Display omitted] [ABSTRACT FROM AUTHOR]