Talsma Wytse, Ye Gang, Liu Yuru, Duim Herman, Dijkstra Sietske, Tran Karolina, Qu Junle, Song Jun, Chiechi Ryan C, Loi Maria Antonietta
Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands.
Center for Biomedical Optics and Photonics (CBOP) & College of Physics and Optoelectronic Engineering, Key Laboratory of Optoelectronic Devices and Systems, Shenzhen University, Shenzhen 518060, PR China.
ACS Appl Mater Interfaces. 2022 Aug 24;14(33):38056-38066. doi: 10.1021/acsami.2c07158. Epub 2022 Aug 9.
Conjugated polymers with narrow band gaps are particularly useful for sorting and discriminating semiconducting single-walled carbon nanotubes (s-SWCNT) due to the low charge carrier injection barrier for transport. In this paper, we report two newly synthesized narrow-band-gap conjugated polymers ( and ) based on naphthalene diimide (NDI) and thienylennevinylene (TVT) building blocks, decorated with different polar side chains that can be used for dispersing and discriminating s-SWCNT. Compared with the mid-band-gap conjugated polymer , which is composed of naphthalene diimide (NDI) and head-to-head bithiophene building blocks, the addition of a vinylene linker eliminates the steric congestion present in head-to-head bithiophene, which promotes backbone planarity, extending the π-conjugation length and narrowing the band gap. Cyclic voltammetry (CV) and density functional theory (DFT) calculations suggest that inserting a vinylene group in a head-to-head bithiophene efficiently lifts the highest occupied molecular orbital (HOMO) level (-5.60 eV for , -5.02 eV for , and -5.09 eV for ). All three polymers are able to select for s-SWCNT, as evidenced by the sharp transitions in the absorption spectra. Field-effect transistors (FETs) fabricated with the polymer:SWCNT inks display p-dominant properties, with higher hole mobilities when using the NDI-TVT polymers as compared with (0.6 cm V s for HiPCO:, 1.5 cm V s for HiPCO:, and 2.3 cm V s for HiPCO:). This improvement is due to the better alignment of the HOMO level of and with that of the dominant SWCNT specie.
由于电荷载流子注入传输势垒低，窄带隙共轭聚合物对于半导体单壁碳纳米管（s - SWCNT）的分类和鉴别特别有用。在本文中，我们报道了两种新合成的基于萘二亚胺（NDI）和噻吩基亚乙烯基（TVT）结构单元的窄带隙共轭聚合物（ 和 ），它们带有不同的极性侧链，可用于分散和鉴别s - SWCNT。与由萘二亚胺（NDI）和头对头联二噻吩结构单元组成的中带隙共轭聚合物相比，亚乙烯基连接基团的加入消除了头对头联二噻吩中存在的空间拥挤，这促进了主链平面性，延长了π共轭长度并缩小了带隙。循环伏安法（CV）和密度泛函理论（DFT）计算表明，在头对头联二噻吩中插入一个亚乙烯基有效地提升了最高占据分子轨道（HOMO）能级（ 为 - 5.60 eV， 为 - 5.02 eV， 为 - 5.09 eV）。所有这三种聚合物都能够对s - SWCNT进行选择，吸收光谱中的急剧转变证明了这一点。用聚合物：SWCNT墨水制备的场效应晶体管（FET）显示出p型主导特性，与 相比，使用NDI - TVT聚合物时具有更高的空穴迁移率（HiPCO： 的为0.6 cm² V⁻¹ s⁻¹， 的为1.5 cm² V⁻¹ s⁻¹， 的为2.3 cm² V⁻¹ s⁻¹）。这种改善是由于 和 的HOMO能级与占主导的SWCNT物种的HOMO能级更好地对齐。
