Publication date: 15th December 2025
Conjugated polymers are key materials in organic electronic technologies, where thermal and mechanical stability strongly affect charge transport, morphological stability, and device lifetime.[1] The glass transition controls chain mobility and relaxation processes, yet how these dynamics emerge and couple across molecular and macromolecular scales remains an open question.[2]
Here, we investigate the glass transition dynamics of a conjugated polymer by combining dynamic mechanical thermal analysis (DMTA) and temperature‑dependent Raman spectroscopy, enabling complementary macromolecular and molecular‑level insights. DMTA probes bulk viscoelastic responses, while Raman spectroscopy sensitively tracks thermally induced changes in molecular vibrations associated with backbone and side‑chain dynamics.
Using this dual approach, we identify two distinct relaxation processes. The α‑relaxation, detected in both DMTA and Raman measurements, is attributed to cooperative segmental motion associated with the glass transition. In addition, a β‑relaxation is observed at lower temperatures, corresponding to localized molecular motions, likely involving side‑chain dynamics. The simultaneous detection of these processes highlights the strong coupling between molecular‑scale motions and macroscopic mechanical behavior.
Our results demonstrate that combining mechanical and spectroscopic techniques provides a powerful framework for understanding relaxation phenomena in conjugated polymers, offering insights relevant for the rational design of thermally stable and mechanically robust organic electronic materials.
The authors acknowledge financial support from the Knut and Alice Wallenberg Foundation (grant agreements with reference numbers 2020.0187 and 2022.0034).
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