Nanotubes from the Misfit Layered Compound (SmS)TaS: Atomic Structure, Charge Transfer, and Electrical Properties.

Misfit layered compounds (MLCs) MX-TX, where M, T = metal atoms and X = S, Se, or Te, and their nanotubes are of significant interest due to their rich chemistry and unique quasi-1D structure. In particular, LnX-TX (Ln = rare-earth atom) constitute a relatively large family of MLCs, from which nanotubes have been synthesized. The properties of MLCs can be tuned by the chemical and structural interplay between LnX and TX sublayers and alloying of each of the Ln, T, and X elements. In order to engineer them to gain desirable performance, a detailed understanding of their complex structure is indispensable. MLC nanotubes are a relative newcomer and offer new opportunities. In particular, like WS nanotubes before, the confinement of the free carriers in these quasi-1D nanostructures and their chiral nature offer intriguing physical behavior. High-resolution transmission electron microscopy in conjunction with a focused ion beam are engaged to study SmS-TaS nanotubes and their cross-sections at the atomic scale. The atomic resolution images distinctly reveal that Ta is in trigonal prismatic coordination with S atoms in a hexagonal structure. Furthermore, the position of the sulfur atoms in both the SmS and the TaS sublattices is revealed. X-ray photoelectron spectroscopy, electron energy loss spectroscopy, and X-ray absorption spectroscopy are carried out. These analyses conclude that charge transfer from the Sm to the Ta atoms leads to filling of the Ta 5 level, which is confirmed by density functional theory (DFT) calculations. Transport measurements show that the nanotubes are semimetallic with resistivities in the range of 10 Ω·cm at room temperature, and magnetic susceptibility measurements show a superconducting transition at 4 K.