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

Zhiyuan Qian; Shaochuan Luo; Tengfei Qu; Luke A. Galuska; Song Zhang; Zhiqiang Cao; Sujata Dhakal; Youjun He; Kunlun Hong; Dongshan Zhou; Xiaodan Gu

doi:10.1557/s43578-020-00062-9

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

Zhiyuan Qian, Shaochuan Luo, Tengfei Qu, Luke A. Galuska, Song Zhang, Zhiqiang Cao, Sujata Dhakal, Youjun He, Kunlun Hong, Dongshan Zhou, Xiaodan Gu

SANS & Spin Echo

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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. [Figure not available: see fulltext.]

Original language	English
Pages (from-to)	191-202
Number of pages	12
Journal	Journal of Materials Research
Volume	36
Issue number	1
DOIs	https://doi.org/10.1557/s43578-020-00062-9
State	Published - Jan 2021

Funding

This work is supported by the USM start?up grant for Z.Q., Z.C., and X.G. S.Z. also acknowledge National Science Foundation (NSF) for partial supported through office of integrative activities (OIA) by NSF OIA?1757220. L.G. thanks NSF DGE for providing support with grant NSF DGE?1449999. The instrument used in this work Flash DSC was acquired with support from ERDC. The polymers were synthesized at the Center for Nanophase Materials Sciences, which is a DOE Office of Science User Facility. S.L., T.Q., and D.Z. thank the National Natural Science Foundation of China (Nos. 21790345 and 51673094) for providing financial support. S. L. thank the Guangdong Basic and Applied Basic Research Foundation(2019A1515110647). This work was funded by the National Science Foundation (NSF OIA‐1757220 and NSF NRT‐1449999) and the National Natural Science Foundation of China (Nos. 21790345 and 51673094). This work is supported by the USM start‐up grant for Z.Q., Z.C., and X.G. S.Z. also acknowledge National Science Foundation (NSF) for partial supported through office of integrative activities (OIA) by NSF OIA‐1757220. L.G. thanks NSF DGE for providing support with grant NSF DGE‐1449999. The instrument used in this work Flash DSC was acquired with support from ERDC. The polymers were synthesized at the Center for Nanophase Materials Sciences, which is a DOE Office of Science User Facility. S.L., T.Q., and D.Z. thank the National Natural Science Foundation of China (Nos. 21790345 and 51673094) for providing financial support. S. L. thank the Guangdong Basic and Applied Basic Research Foundation(2019A1515110647).

Keywords

conjugated polymer
fast scanning chip calorimetry
isothermal crystallization kinetics

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10.1557/s43578-020-00062-9

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title = "Influence of side‐chain isomerization on the isothermal crystallization kinetics of poly(3‐alkylthiophenes)",

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. [Figure not available: see fulltext.]",

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author = "Zhiyuan Qian and Shaochuan Luo and Tengfei Qu and Galuska, \{Luke A.\} and Song Zhang and Zhiqiang Cao and Sujata Dhakal and Youjun He and Kunlun Hong and Dongshan Zhou and Xiaodan Gu",

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doi = "10.1557/s43578-020-00062-9",

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T1 - Influence of side‐chain isomerization on the isothermal crystallization kinetics of poly(3‐alkylthiophenes)

AU - Qian, Zhiyuan

AU - Luo, Shaochuan

AU - Qu, Tengfei

AU - Galuska, Luke A.

AU - Zhang, Song

AU - Cao, Zhiqiang

AU - Dhakal, Sujata

AU - He, Youjun

AU - Hong, Kunlun

AU - Zhou, Dongshan

AU - Gu, Xiaodan

PY - 2021/1

Y1 - 2021/1

N2 - 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. [Figure not available: see fulltext.]

AB - 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. [Figure not available: see fulltext.]

KW - conjugated polymer

KW - fast scanning chip calorimetry

KW - isothermal crystallization kinetics

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M3 - Article

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

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