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Influence of side-chain isomerization on the isothermal crystallization kinetics of poly(3-alkylthiophenes)

Published online by Cambridge University Press:  07 September 2020

Zhiyuan Qian ,
Shaochuan Luo ,
Tengfei Qu ,
Luke A. Galuska ,
Song Zhang ,
Zhiqiang Cao ,
Sujata Dhakal ,
Youjun He ,
Kunlun Hong  and
Dongshan Zhou
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Zhiyuan Qian
Affiliation:
School of Polymer Science and Engineering, Center for Optoelectronic Materials and Devices, The University of Southern Mississippi, Hattiesburg, Mississippi39406, USA
Shaochuan Luo
Affiliation:
Department of Polymer Science and Engineering, School of Chemistry and Chemical Engineering, Key Laboratory of High Performance Polymer Materials and Technology of Ministry of Education, and The State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing210093, P.R. China
Tengfei Qu
Affiliation:
Department of Polymer Science and Engineering, School of Chemistry and Chemical Engineering, Key Laboratory of High Performance Polymer Materials and Technology of Ministry of Education, and The State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing210093, P.R. China
Luke A. Galuska
Affiliation:
School of Polymer Science and Engineering, Center for Optoelectronic Materials and Devices, The University of Southern Mississippi, Hattiesburg, Mississippi39406, USA
Song Zhang
Affiliation:
School of Polymer Science and Engineering, Center for Optoelectronic Materials and Devices, The University of Southern Mississippi, Hattiesburg, Mississippi39406, USA
Zhiqiang Cao
Affiliation:
School of Polymer Science and Engineering, Center for Optoelectronic Materials and Devices, The University of Southern Mississippi, Hattiesburg, Mississippi39406, USA
Sujata Dhakal
Affiliation:
School of Polymer Science and Engineering, Center for Optoelectronic Materials and Devices, The University of Southern Mississippi, Hattiesburg, Mississippi39406, USA
Youjun He
Affiliation:
Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, Tennessee37831, USA
Kunlun Hong
Affiliation:
Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, Tennessee37831, USA Department of Chemical and Biomolecular Engineering, University of Tennessee, Knoxville, Tennessee37996, USA
Dongshan Zhou
Affiliation:
Department of Polymer Science and Engineering, School of Chemistry and Chemical Engineering, Key Laboratory of High Performance Polymer Materials and Technology of Ministry of Education, and The State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing210093, P.R. China
Xiaodan Gu*
Affiliation:
School of Polymer Science and Engineering, Center for Optoelectronic Materials and Devices, The University of Southern Mississippi, Hattiesburg, Mississippi39406, USA
*
a)Address all correspondence to this author. e-mail: xiaodan.gu@usm.edu
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Abstract

Flexible alkyl side chain in conjugate polymers (CPs) improves the solubility and promotes solution processability, in addition, it affects interchain packing and charge mobilities. Despite the well-known charge mobility and morphology correlation for these semi-crystalline polymers, there is a lack of fundamental understanding of the impact of side chain on their crystallization kinetics. In the present work, isothermal crystallization of five poly(3-alkylthiophene-2,5-diyl) (P3ATs) with different side-chain structures were systematically investigated. To suppress the extremely fast crystallization and trap the sample into amorphous glass, an advanced fast scanning chip calorimetry technique, which is able to quench the sample with few to tens thousands of K/s, was applied. Results show that the crystallization of P3ATs was greatly inhibited after incorporation of branched side chains, as indicated by a dramatic up to six orders of magnitude decrease in the crystallization rate. The suppressed crystallization of P3ATs were correlated with an increased π–π stacking distance due to unfavorable side-chain steric interaction. This work provides a pathway to use side-chain engineering to control the crystallization behavior for CPs, thus to control device performance.

Keywords

conjugated polymerfast scanning chip calorimetryisothermal crystallization kinetics

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Type
Invited Feature Paper
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Journal of Materials Research , First View , pp. 1 - 12
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Copyright © Materials Research Society 2020

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Footnotes

b)

These authors contributed equally.

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