Issue 1, 2024

Real-time correlation of crystallization and segmental order in conjugated polymers

Abstract

Modulating the segmental order in the morphology of conjugated polymers is widely recognized as a crucial factor for achieving optimal electronic properties and mechanical deformability. However, it is worth noting that the segmental order is typically associated with the crystallization process, which can result in rigid and brittle long-range ordered crystalline domains. To precisely control the morphology, a comprehensive understanding of how highly anisotropic conjugated polymers form segmentally ordered structures with ongoing crystallization is essential, yet currently elusive. To fill this knowledge gap, we developed a novel approach with a combination of stage-type fast scanning calorimetry and micro-Raman spectroscopy to capture the series of specimens with a continuum in the polymer percent crystallinity and detect the segmental order in real-time. Through the investigation of conjugated polymers with different backbones and side-chain structures, we observed a generally existing phenomenon that the degree of segmental order saturates before the maximum crystallinity is achieved. This disparity allows the conjugated polymers to achieve good charge carrier mobility while retaining good segmental dynamic mobility through the tailored treatment. Moreover, the crystallization temperature to obtain optimal segmental order can be predicted based on Tg and Tm of conjugated polymers. This in-depth characterization study provides fundamental insights into the evolution of segmental order during crystallization, which can aid in designing and controlling the optoelectronic and mechanical properties of conjugated polymers.

Graphical abstract: Real-time correlation of crystallization and segmental order in conjugated polymers

Supplementary files

Article information

Article type
Communication
Submitted
22 Jun 2023
Accepted
28 Sep 2023
First published
04 Okt 2023

Mater. Horiz., 2024,11, 196-206

Author version available

Real-time correlation of crystallization and segmental order in conjugated polymers

S. Luo, Y. Li, N. Li, Z. Cao, S. Zhang, M. U. Ocheje, X. Gu, S. Rondeau-Gagné, G. Xue, S. Wang, D. Zhou and J. Xu, Mater. Horiz., 2024, 11, 196 DOI: 10.1039/D3MH00956D

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