Semiconducting single-walled carbon nanotubes sorting with a removable solubilizer based on dynamic supramolecular coordination chemistry

Abstract

Highly pure semiconducting single-walled carbon nanotubes (SWNTs) are essential for the next generation of electronic devices, such as field-effect transistors and photovoltaic applications; however, contamination by metallic SWNTs reduces the efficiency of their associated devices. Here we report a simple and efficient method for the separation of semiconducting-and metallic SWNTs based on supramolecular complex chemistry. We here describe the synthesis of metal-coordination polymers (CP-Ms) composed of a fluorene-bridged bis-phenanthroline ligand and metal ions. On the basis of a difference in the 'solubility product' of CP-M-solubilized semiconducting SWNTs and metallic SWNTs, we readily separated semiconducting SWNTs. Furthermore, the CP-M polymers on the SWNTs were simply removed by adding a protic acid and inducing depolymerization to the monomer components. We also describe molecular mechanics calculations to reveal the difference of binding and wrapping mode between CP-M/semiconducting SWNTs and CP-M/metallic SWNTs. This study opens a new stage for the use of such highly pure semiconducting SWNTs in many possible applications.

Thickness-dependent thermoelectric power factor of polymer-functionalized semiconducting carbon nanotube thin films

“…Particularly, film thickness should be considered in the analysis of transport in insulator-wrapped s-SWNT films. Our results could be used in materials design strategies including surfactant removal [35,36], dopant miscibility [37], and thin film integration [38]. …”

Assembly and Electronic Applications of Colloidal Nanomaterials

“…Recently, liquid-exfoliated monolayer WS 2 has been enriched in this way by centrifuging the as-sonicated dispersions at a series of speeds. [154][155][156][157][158][159][160][161][162] These polymers have achieved varying levels of success in sorting CoMoCAT, HiPco, laser ablation, and arc-discharge SWCNTs due to their different ranges of diameters. For example, gradual injection of poor solvents has been used to lower the stability of nanocrystals to yield size-selective precipitation.…”

“…Polyfluorene and polythiophene derivatives or copolymers have been heavily investigated to target specific chiralities of SWCNTs. [167] Another strategy incorporates sacrificial bonds, such as coordination bonds, [156] hydrogen bonds, [168] or imine bonds, [157] in polyfluorene-based supramolecular copolymers. [159] In the best case, semiconducting SWCNTs with greater than 99% purity have been isolated by this approach.…”

“…[154][155][156][157][158][159][160][161][162] These polymers have achieved varying levels of success in sorting CoMoCAT, HiPco, laser ablation, and arc-discharge SWCNTs due to their different ranges of diameters. [156,157,168] Density-gradient ultracentrifugation (DGU), developed initially for biochemistry, [149,169] is another separation strategy based on centrifugation, which utilizes density-gradient media to influence the motion of nanomaterials in centrifugal fields. [157,161] In addition, single-handedness SWCNT enantiomers have been separated using conjugated polymers with chiral moieties.…”

Selective Interaction of a Water Soluble Naphthalenediimide with Single-Walled Carbon Nanotubes

“…Although several methods for the selective synthesis of specific types of SWCNTs have been devised, there are still problems of size heterogeneity. Therefore, post growth separation approaches, such as density gradient ultracentrifugation, 9 electrophoresis, 10 chromatography 11 and molecule assisted selective extractions [12][13][14] are currently employed to minimize size dispersion. While the use of n-type semiconductors for selective adsorption on SWCNTs have been successfully reported, 15,16 here we discuss the non-covalent interaction of a water soluble naphthalenediimide derivative (NDI1) with SWCNTs.…”