Multiamorphous Phases in Diketopyrrolopyrrole-Based Conjugated Polymers: From Bulk to Ultrathin Films

Luo, Shaochuan; Wang, Tianyi; Ocheje, Michael U.; Zhang, Song; Xu, Jie; Qian, Zhiyuan; Gu, Xiaodan; Xue, Gi; Rondeau-Gagné, Simon; Jiang, Jing; Hu, Wenbing; Zhuravlev, Evgeny; Zhou, Dongshan

doi:10.1021/acs.macromol.9b02738

Multiamorphous Phases in Diketopyrrolopyrrole-Based Conjugated Polymers: From Bulk to Ultrathin Films

Journal Article · Tue May 26 00:00:00 EDT 2020 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.9b02738· OSTI ID:1659428

Luo, Shaochuan ^[1]; Wang, Tianyi ^[2]; Ocheje, Michael U. ^[3]; Zhang, Song ^[4]; Xu, Jie ^[5]; Qian, Zhiyuan ^[4]; ^[4]; Xue, Gi ^[2]; ^[3]; Jiang, Jing ^[2]; ^[2]; Zhuravlev, Evgeny ^[2]; ^[2]

Nanjing Univ. (China); Peking Univ., Beijing (China); University of Southern Mississippi
Nanjing Univ. (China)
Univ. of Windsor, ON (Canada)
Univ. of Southern Mississippi, Hattiesburg, MI (United States)
Argonne National Lab. (ANL), Lemont, IL (United States)

The glass transition temperature (T_g) of conjugated polymers is a crucial physical parameter that governs their mechanical and electrical properties for applications from sensor technology to skin-like electronics. Despite some well-developed methods that exist for detecting T_g of conjugated polymers, there is still a need for the combination of advanced calorimetric methodologies to characterize T_g in a broad range of temperatures and scales from bulk to nanometer-thin films. In this work, alternating current (ac) chip calorimetry and flash differential scanning calorimetry (flash DSC) are applied to successfully identify the Tgs and segmental relaxations of conjugated polymers. The detected relaxations were interpreted, in agreement with existing observations in similar systems, as a side-chain relaxation (low temperature), mobile amorphous fractions (MAF), and rigid amorphous fractions (RAF). T_gs of MAF and RAF increase and decrease with increasing size of fused thiophene units in the backbone, respectively. The T_gs of diketopyrrolopyrrole-based conjugated polymer thin films are also identified by the same method, with both T_gs showing a decreased value compared to those of bulk samples. Furthermore, the weight fractions of MAF and RAF with various film thicknesses are qualitatively analyzed based on the heat capacity step of each amorphous fraction during the glass transition. This facile method gives insights into the physical nature of amorphous phases in conjugated polymers for better revealing their structure-property relationships, which will guide the designs of new materials with optimized electrical and mechanical properties in the future.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Southern Mississippi, Hattiesburg, MI (United States); Univ. of Southern Mississippi, Hattiesburg, MS (United States); University of Southern Mississippi, Hattiesburg, MS (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0019361

OSTI ID:: 1659428

Alternate ID(s):: OSTI ID: 1774343
OSTI ID: 1985345

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 11 Vol. 53; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Multiamorphous Phases in Diketopyrrolopyrrole-Based Conjugated Polymers: From Bulk to Ultrathin Films

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