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Harnessing Thin-Film Polymorphism via Regulating Conjugated Polymer-Solvent Interactions for Organic Field-Effect
Hao Zheng1, Yanan Guo1, Yan Guan1
1State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, Shanghai 200438, China.
Nano Letters
|April 1, 2026
Summary
Controlling conjugated polymer structures, like poly(3-hexylselenophene) (P3HS), in thin films is key for better optoelectronics. This study links polymer interactions in solution to film structures and charge transport properties.
Area of Science:
- Materials Science
- Polymer Chemistry
- Organic Electronics
Background:
- Tailoring polymorphism in conjugated polymers is crucial for advancing optoelectronic device performance.
- A deep understanding of polymorphism formation and transformation mechanisms is currently lacking.
- Poly(3-hexylselenophene) (P3HS) is a model conjugated polymer with potential applications in organic electronics.
Purpose of the Study:
- To establish a correlation between thin-film polymorphisms of P3HS and its solution-state interactions.
- To investigate the influence of polymer-polymer and polymer-solvent interactions on P3HS thin-film structures.
- To elucidate the impact of different P3HS polymorphs on charge transport properties.
Main Methods:
- Quantification of the second virial coefficient (A2) to assess polymer-solvent and polymer-polymer interactions.
- Solution processing of P3HS in different solvents (toluene and p-xylene) with varying evaporation rates.
- Analysis of thin-film polymorphisms formed under different solution conditions.
- Measurement of charge transport characteristics (e.g., charge mobility) for different polymorphs.
Main Results:
- P3HS exhibits weak aggregation in toluene (positive A2), dominated by polymer-solvent interactions, leading to polymorph I in films due to fast evaporation.
- P3HS shows strong aggregation in p-xylene (negative A2), driven by polymer-polymer interactions, resulting in polymorph II formation with slower evaporation.
- Polymorph I demonstrates significantly higher charge mobility compared to polymorph II.
- A direct link is established between molecular interactions in solution, aggregate formation, and resulting thin-film polymorphisms.
Conclusions:
- Solution-state interactions critically dictate the thin-film polymorphism of conjugated polymers like P3HS.
- Controlling solvent choice and evaporation rate allows for targeted formation of specific P3HS polymorphs.
- The identified P3HS polymorphs exhibit distinct charge transport properties, offering a pathway for optimizing organic electronic devices.
