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The nanoscale structure and macroscopic morphology of π-conjugated polymers are very important for their electronic application. While ordered single crystals of small molecules have been obtained via solution deposition, macroscopically aligned films of π-conjugated polymers deposited directly from solution have always required surface modification or complex pre-deposition processing of the solution. Here, ordered nanowires were obtained via shear-enhanced crystallization of π-conjugated polymers at the air–liquid–solid interface using simple deposition of the polymer solution onto an inclined substrate. The formation of macroscopically aligned nanowire arrays was found to be due to the synergy between intrinsic (π-conjugated backbone) and external (crystallization conditions) effects. The oriented nanowires showed remarkable improvement in the charge carrier mobility compared to spin-coated films as characterized in organic field-effect transistors (OFETs). Considering the simplicity and large-scale applicability, shear-enhanced crystallization of π-conjugated polymers provides a promising strategy to achieve high-performance polymer semiconductor films for electronics applications.
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Design rules for dynamic-template-directed crystallization of conjugated polymers
The multiscale morphology and device performance of printed semiconducting polymers are highly sensitive to the substrate/ink interfacial properties during solution coating. There is an urgent need for general design rules correlating the substrate properties and conjugated polymer (CP) morphology, which do not yet exist. Dynamic surfaces are particularly promising for templating highly crystalline and highly aligned conjugated polymer thin films and have been shown in recent studies. Herein, we implement the dynamic-templating method using a series of liquid-infused nanoporous substrates as a tool to study the impact of template reconfigurability and chemistry on the multiscale morphology of conjugated polymer thin films, using a high performing donor–acceptor polymer (DPP-BTz) as a model compound. By quantifying the enthalpy of adsorption, we demonstrate that the strength of template–CP interactions directly measures the effectiveness of dynamic surfaces in promoting conjugated polymer crystallization and alignment. We further show that the enthalpy of interactions increases by enhancing the template dynamics and is sensitively modulated by template chemistry. Specifically, increasing the template–CP interactions leads to a larger domain size and higher degree of crystallinity in templated conjugated polymer thin films prepared by meniscus-guided solution coating. This observation validates our hypothesis that dynamic templates function by promoting the nucleation of conjugated polymers. We also demonstrate that such dynamic-template-dependent morphology is independent of coating speed. Notably, the enhanced morphological properties modulate the charge carrier mobility in field-effect transistors (FETs) over an order of magnitude reaching a hole mobility of 2.8 cm 2 V −1 s −1 . This work is a significant step towards establishing general guidelines on how the substrate–ink interfacial properties influence morphology and performance of solution coated CP thin films.
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- PAR ID:
- 10134470
- Date Published:
- Journal Name:
- Molecular Systems Design & Engineering
- Volume:
- 5
- Issue:
- 1
- ISSN:
- 2058-9689
- Page Range / eLocation ID:
- 125 to 138
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/C9ME00042A
