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Poly(3-alkylthiophene)-block-poly(3-alkylselenophene)s : Conjugated Diblock Co-polymers with Atypical Self-Assembly Behavior

Title data

Kynaston, Emily L. ; Winchell, K. J. ; Yee, Patrick Y. ; Manion, Joseph G. ; Hendsbee, Arthur D. ; Li, Yuning ; Hüttner, Sven ; Tolbert, Sarah H. ; Seferos, Dwight S.:
Poly(3-alkylthiophene)-block-poly(3-alkylselenophene)s : Conjugated Diblock Co-polymers with Atypical Self-Assembly Behavior.
In: ACS Applied Materials & Interfaces. Vol. 11 (20 February 2019) Issue 7 . - pp. 7174-7183.
ISSN 1944-8252
DOI: https://doi.org/10.1021/acsami.8b18795

Abstract in another language

Understanding self-assembly behavior and resulting morphologies in block co-polymer films is an essential aspect of chemistry and materials science. Although the self-assembly of amorphous coil–coil block co-polymers is relatively well understood, that of semicrystalline block co-polymers where each block has distinct crystallization properties remains unclear. Here, we report a detailed study to elucidate the rich self-assembly behavior of conjugated thiophene–selenophene (P3AT-b-P3AS) block co-polymers. Using a combination of microscopy and synchrotron-based X-ray techniques, we show that three different film morphologies, denoted as lamellae, co-crystallized fibers, and patchy fibers, arise from the self-assembly of these block co-polymers over a relatively narrow range of overall degrees of polymerization (30 < N < 90). Crystallization-driven phase separation occurs at a very low N (<35), and lamellar films are formed. Conversely, at medium N (50–60) and high N (>80), the thiophene and selenophene blocks co-crystallize into nanofibers, where medium N leads to much more mixing than high N. The overall tendency for phase separation in these systems follows rather different trends than phase separation in amorphous polymers in that we observe the greatest degree of phase separation at the lowest N. Finally, we demonstrate how each morphology influences transport properties in organic thin-film transistors comprised of these conjugated polymers.Understanding self-assembly behavior and resulting morphologies in block co-polymer films is an essential aspect of chemistry and materials science. Although the self-assembly of amorphous coil–coil block co-polymers is relatively well understood, that of semicrystalline block co-polymers where each block has distinct crystallization properties remains unclear. Here, we report a detailed study to elucidate the rich self-assembly behavior of conjugated thiophene–selenophene (P3AT-b-P3AS) block co-polymers. Using a combination of microscopy and synchrotron-based X-ray techniques, we show that three different film morphologies, denoted as lamellae, co-crystallized fibers, and patchy fibers, arise from the self-assembly of these block co-polymers over a relatively narrow range of overall degrees of polymerization (30 < N < 90). Crystallization-driven phase separation occurs at a very low N (<35), and lamellar films are formed. Conversely, at medium N (50–60) and high N (>80), the thiophene and selenophene blocks co-crystallize into nanofibers, where medium N leads to much more mixing than high N. The overall tendency for phase separation in these systems follows rather different trends than phase separation in amorphous polymers in that we observe the greatest degree of phase separation at the lowest N. Finally, we demonstrate how each morphology influences transport properties in organic thin-film transistors comprised of these conjugated polymers.

Further data

Item Type: Article in a journal
Refereed: Yes
Institutions of the University: Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry > Junior Professorship Solar Energy > Junior Professorship Solar Energy - Juniorprof. Dr. Sven Hüttner
Profile Fields > Advanced Fields > Polymer and Colloid Science
Result of work at the UBT: Yes
DDC Subjects: 500 Science > 530 Physics
500 Science > 540 Chemistry
Date Deposited: 27 Sep 2019 09:06
Last Modified: 27 Sep 2019 09:06
URI: https://eref.uni-bayreuth.de/id/eprint/52488