Macroscopic yarns of FeCl$_{3}$-intercalated collapsed carbon nano-tubes with high doping and stability

TL;DR

This paper demonstrates stable FeCl3 intercalation into macroscopic collapsed carbon nanotube fibers, significantly increasing their charge carrier concentration and electrical conductivity, with detailed structural and electronic characterization.

Contribution

It reports the first observation of long FeCl3 crystals in intercalated CNT fibers and their stability, along with detailed analysis of charge transfer and electronic properties.

Findings

FeCl3 forms elongated crystals in CNT fibers

Intercalation increases conductivity sixfold

Stable intercalation persists for months in ambient conditions

Abstract

Macroscopic arrays of highly crystalline nanocarbons offer the possibility of modifying the electronic structure of their low dimensional constituents, for example through doping, and studying the resulting collective bulk behaviour. Insertion of electron donors or acceptors between graphitic layers is an attractive method to reversibly increase charge carrier concentra-tion without disruption of the sp$2$-conjugated system. This work demonstrates FeCl$_{3}$ intercalation into fibres made up of collapsed (flattened) carbon nanotubes. The bundles of collapsed CNTs, similar to crystallites of graphitic nanoribbons, host elongated layered FeCl$_{3}$ crystals of hundreds of $nm$ long, much longer than previous reports on graphitic materials and directly observable by transmission electron microscopy and X-ray diffraction. Intercalated CNT fibres remain stable after months of exposure to ambient conditions, partly due to the spontaneous formation of passivating monolayers of FeClO at the crystal edge, preventing both desorption of intercalant and further hydrolysis. Raman spectroscopy shows substantial electron transfer from the CNTs to FeCl$_{3}$, a well-known acceptor, as observed by G band upshifts as large as $25 cm^{-1}$. After resolving Raman features for the inner and outer layers of the collapsed CNTs, strain and dynamic effect contributions of charge transfer to the Raman upshift could be decoupled, giving a Fermi level downshift of $- 0.72 eV$ and a large average free carrier concentration of $5.3X10^{13}$ $cm^{-2}$ ($0.014$ electrons per carbon atom) in the intercalated system. Four-probe resistivity measurements show an increase in conductivity by a factor of six upon intercalation