Nikolai A. Kiselev

HRTEM and HAADF STEM of 1DTbBr_x@SWCNT meta‐nanotubes reveal three structural modifications of 1D nanocrystals within single wall carbon nanotube channels attributed to a different stoichiometry of the guest crystal. For SWCNTs with diameters D_m > 1.4 nm a most complete tetragonal unit cell is observed. When crystallization occurs inside SWCNT with D_m < 1.4 nm 1D TbBr_x crystal deforms a nanotube to elliptical shape in cross section. In this case the 1D crystal unit cell becomes monoclinic, with possible loss of a part of bromine atoms. Two modifications of a monoclinic unit cell appear. One of them is characterized by single or pair vacancies in the structure of the 1D crystal. Another structure is explained by peripheral and central bromine atoms loss. An appearance of such modifications can be stimulated by electron irradiation. The loss of bromine atoms is in agreement with chemical analysis data. Electronic properties of obtained meta‐nanotubes are investigated using optical absorption and Raman spectroscopy. It is shown that intercalation of terbium bromide into SWCNTs leads to acceptor doping of SWCNTs. According to local EDX analysis and elemental mapping this doping can arise from significant stoichiometry change in 1D nanocrystal indicating an average Tb:Br atomic ratio of 1:2.8 ± 0.1.

The method for imaging of highly sensitive nanostructures unstable under electron beam irradiation is introduced. To reduce charge and thermally generated beam damage, highly conductive multilayered graphene or thin graphite layers were used as supports for nanostructures. Well-defined crystalline structure of graphite layers enables image reconstruction by Fourier filtering and allows maintaining high quality of images. The approach was tested for imaging of highly sensitive quasi one-dimensional SnTe nanocrystals hosted inside single-walled carbon nanotubes. Relying on the filtered images and the image simulation, the structure of one-dimensional SnTe was established as a chain of fcc NaCl type unit cells, connected by the [001] edges with direction coinciding with nanotube axis.

Summary: Nanocomposites consisting of one‐dimensional (1D) crystals of the cationic conductors CuI, CuBr and AgBr inside single‐walled carbon nanotubes, mainly (n, 0), were obtained using the capillary technique. 1D crystal structure models were proposed based on the high resolution transmission electron microscopy performed on a FEI Titan 80–300 at 80 kV with aberration correction. According to the models and image simulations there are two modifications of 1D crystal: hexagonal close‐packed bromine (iodine) anion sublattice (growth direction ) and 1D crystal cubic structure (growth direction ) compressed transversely to the nanotube (D_m∼1.33 nm) axis. Tentatively this kind of 1D crystal can be considered as monoclinic. One modification of the anion sublattice reversibly transforms into the other inside the nanotube, probably initiated by electron beam heating. As demonstrated by micrographs, copper or silver cations can occupy octahedral positions or are statistically distributed across two tetrahedral positions. A 1DAgBr@SWNT (18, 0; 19, 0) pseudoperiodic ‘lattice distortion' is revealed resulting from convolution of the nanotube wall function image with 1D cubic crystal function image.