Highly Efficient Preparation of Length and Width-Controllable Donor-Acceptor Nanoribbons via Polymerization-Induced Crystallization-Driven Self-Assembly of Fully Conjugated Block Copolymers
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2024-07-31
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Journal Article
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Abstract
Despite the high potential of one-dimensional (1D) donor–acceptor (D–A) coaxial nanostructures in bulk-heterojunction solar cell applications, the preparation of such 1D nanostructures using π-conjugated polymers has remained elusive. Herein, we demonstrate the first example of D–A semiconducting nanoribbons based on fully conjugated block copolymers (BCPs) prepared in a highly efficient procedure with controllable width and length via living crystallization-driven self-assembly (CDSA). Initially, Suzuki–Miyaura catalyst-transfer polymerization was employed to successfully synthesize BCPs containing two types of acceptor shells as the first block, followed by a donor poly(3-propylthiophene) core as the second block. The limited solubility and high crystallinity of the core induced a polymerization-induced crystallization-driven self-assembly (PI-CDSA) of the BCPs into nanoribbons during polymerization, providing a tunable width (7.6–39.6 nm) depending on the length of the polymer backbone. Surprisingly, purifying as-synthesized BCPs via simple precipitation directly yielded short and uniform seed structures, greatly shortening the overall protocol by eliminating the time-consuming process of initial aging and breaking down to the seed required for the conventional CDSA. With this new highly efficient method, we achieved length control over a broad range from 169 to 2210 nm, with high precision (Lw/Ln < 1.20). Furthermore, combining self-seeding and seeded growth from two different D–A-type BCPs enabled continuous living epitaxial growth from each end of the nanoribbons, resulting in B-A-B triblock D–A semiconducting comicelles with controlled length.
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146 (30)
Pages / Article No.
20750 - 20757
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American Chemical Society
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Subject
Imaging; Nanostructures; Self Organization; Transmission Electron Microscopy; Two Dimensional Materials
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09767 - Choi, Tae-Lim / Choi, Tae-Lim