Variable-Temperature Scattering and Spectroscopy Characterizations for Temperature-Dependent Solution Assembly of PffBT4T-Based Conjugated Polymers

Cao, Zhiqiang; Ma, Guorong; Leng, Mingwan; Zhang, Song; Chen, Jihua; Do, Changwoo; Hong, Kunlun; Fang, Lei; Gu, Xiaodan

doi:10.1021/acsapm.1c01511

Variable-Temperature Scattering and Spectroscopy Characterizations for Temperature-Dependent Solution Assembly of PffBT4T-Based Conjugated Polymers

Journal Article · Wed Feb 09 00:00:00 EST 2022 · ACS Applied Polymer Materials

DOI:https://doi.org/10.1021/acsapm.1c01511· OSTI ID:1888900

Cao, Zhiqiang ^[1]; Ma, Guorong ^[1]; Leng, Mingwan ^[2]; ^[1]; ^[3]; ^[3]; ^[3]; ^[2]; ^[1]

University of Southern Mississippi, Hattiesburg, MS (United States)
Texas A & M University, College Station, TX (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

The solution structure of conjugated polymers (CPs) from which the films are cast is critical for tailoring the thin-film morphology thus device performance. Here, we used multimodal variable-temperature scattering and spectroscopy tools to fully quantify the solution assembly of poly[(5,6-difluoro-2,1,3-benzothiadiazol-4,7-diyl)-alt-(3,3'''-dialkyl-2,2';5',2'';5'',2'''-quaterthiophen-5,5'''-diyl)] (PffBT4T) polymers with varying side-chain lengths at different assembly temperatures. The conformational and aggregation behaviors for PffBT4T-based CPs were found to be very sensitive to both temperature and side chain length using ultraviolet–visible (UV–vis) spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, dynamic light scattering (DLS), and small-angle neutron scattering (SANS). We found that with slightly increasing side chain length from 2-octyldodecyl (C8C12) to 2-nonyltridecyl (C9C13), PffBT4T-based CPs show a significant decrease in aggregation-to-dissolved chain transition temperature (10 °C), degree of aggregation, enthalpy change of aggregation, and size of the aggregates in solution. At room temperature, PffBT4T polymer strongly aggregated to form fabric structure with the film thickness of a few nanometers in thickness and hundreds of nanometers in length, as probed by atomic force microscopy (AFM), transmission electronic microscopy (TEM), and dynamic light scattering (DLS). At the elevated temperature above the aggregation-to-dissolved chain transition temperature, PffBT4T is fully dissolved and adopts a semiflexible coil conformation with the persistence length of 3.1 nm for PffBT4T-C8C12 and a slightly increased persistence length of 3.4 nm for PffBT4T-C9C13, according to temperature-dependent SANS measurements. Longer side chains of PffBT4T-C9C13 also lead to less aggregation enthalpy gain compared with PffBT4T-C8C12. This work provides a solution structure manipulating strategy of CPs and thus will inspire the molecular design and processing protocols of CPs toward higher performance electronic devices.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1888900

Journal Information:: ACS Applied Polymer Materials, Journal Name: ACS Applied Polymer Materials Journal Issue: 5 Vol. 4; ISSN 2637-6105

Publisher:: ACS PublicationsCopyright Statement

Country of Publication:: United States

Language:: English

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