High Dielectric Constant Semiconducting Poly(3-alkylthiophene)s from Side Chain Modification with Polar Sulfinyl and Sulfonyl Groups

Wang, Chunlai; Zhang, Zhongbo; Pejić, Sandra; Li, Ruipeng; Fukuto, Masafumi; Zhu, Lei; Sauvé, Geneviève

doi:10.1021/acs.macromol.8b01895

Title: High Dielectric Constant Semiconducting Poly(3-alkylthiophene)s from Side Chain Modification with Polar Sulfinyl and Sulfonyl Groups

Journal Article · 14 November 2018 · Macromolecules

DOI: https://doi.org/10.1021/acs.macromol.8b01895 · OSTI ID:1491148

^[1];

^[1]; Pejić, Sandra ^[1]; Li, Ruipeng ^[2]; Fukuto, Masafumi ^[2];

^[1];

^[1]

Case Western Reserve Univ., Cleveland, OH (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)

In this paper, there is growing interest in designing and developing high dielectric constant (ε_r) organic semiconductors because they have the potential to further enhance device performance by promoting exciton dissociation, reducing bimolecular charge carrier recombination, and potentially enhancing charge carrier mobility via charge screening. In this study, a new class of semiconducting polymers with high ε_r, i.e., sulfinylated and sulfonylated poly(3-alkylthiophene)s (P3ATs), were synthesized. Because of efficient rotation of highly polar methylsulfinyl and methylsulfonyl side groups (i.e., orientational polarization), high ε_r values were achieved for these functionalized P3ATs based on an accurate capacitance measurement using a gold/semiconducting polymer/SiO₂/n-doped Si configuration. For example, the ε_r at megahertz and room temperature increased from 3.75 for the regioregular poly(3-hexylthiophene) (P3HT) to 7.4 for the sulfinylated and 8.1–9.3 for sulfonylated P3AT polymers. These values are among the highest ε_r reported for conjugated polymers so far. Grazing-incident wide-angle X-ray diffraction results showed that these polar groups decreased the crystallinity for the polythiophene backbones and interfered with the π–π stacking in the crystalline structure. Consequently, their optical properties, including UV–vis absorption and fluorescence, changed in thin films. From this study, the sulfinylated polymer may be promising to provide a balance between high ε_r and preserving favorable polythiophene π–π stacking structure for device applications.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

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

Grant/Contract Number:: SC0012704

OSTI ID:: 1491148

Report Number(s):: BNL-210851-2019-JAAM

Journal Information:: Macromolecules, Vol. 51, Issue 22; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 37 works

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Title: High Dielectric Constant Semiconducting Poly(3-alkylthiophene)s from Side Chain Modification with Polar Sulfinyl and Sulfonyl Groups

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