Efficient Selective Sorting of Semiconducting Carbon Nanotubes Using Ultra-Narrow-Band-Gap Polymers.

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.