Quasi free-standing one-dimensional nanocrystals of PbTe grown in 1.4 nm SWNTs

Here, we show successful filling of 1.4 nm single-walled carbon nanotubes (SWNT) with PbTe nanocrystals. The structure of one-dimensional PbTe in SWNT was determined using high-resolution transmission electron microscopy (HRTEM). The electronic structure of composites was studied by optical absorbance and Raman spectroscopies indicating no noticeable interaction of encapsulated PbTe with SWNT wall. Experimental data are supported by ab-initio calculations, showing non-zero density of states at the Fermi level of PbTe@SWNT(10,10) provided by both SWNT and PbTe states and thus metallic conductivity of the composite

Spectroelectrochemistry of intercalated single-walled carbon nanotubes

The method of Raman spectroelectrochemical detection of charge transfer in doped single-walled carbon nanotubes is suggested and tested for the determination of the electronic structure of 1D crystal@SWNT composites. Spectroelectrochemical study of CuCl@SWNT composites in resonant Raman conditions revealed a significant Kohn anomaly shift of ca. -0.7 eV corresponding to redox doping of metallic 1.4 nm nanotubes and related to Fermi level downshift. The obtained results are consistent with data available from XPS and optical spectroscopy. (C) 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinhei

The structure and continuous stoichiometry change of 1DTbBr(x)@SWCNTs

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 TbBrx 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 structure and continuous stoichiometry change of 1DTbBr x

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 TbBrx 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

Capsulate structure effect on SWNTs doping in RbxAg1-xI@SWNT composites

The paper reports the relationship between single-walled carbon nanotube (SWNT) doping and capsulate crystal structure in RbxAg1−xI@SWNT composites. The structures of one dimensional (1D) RbI, AgI and RbAg4I5 crystals inside single-walled carbon nanotubes were established by high-resolution transmission electron microscopy (HRTEM) and high-resolution scanning transmission electron microscopy (HAADF HRSTEM), and confirmed by image simulation. Opposite to one-dimensional RbI and AgI, inheriting the structure of bulk analogues, 1D RbAg4I5 forms a new phase within a confined space of the SWNT channel, which differs from the bulk RbAg4I5 structure and can be described by a deformed cubic 1D lattice. X-ray absorption, XPS, optical absorption and Raman spectroscopies were used for comprehensive study of the composites' electronic structures. The study reveals the donor behavior of RbI capsulate and the acceptor behavior of RbAg4I5 and AgI. Quantification of doping levels indicated the prevalence of the effect of the chemical composition of the capsulate on the overall doping efficiency, while a structural effect is mostly prominent in potential distribution on nanotube walls and partial charges on SWNT atoms.This work was supported by the Helmholtz Zentrum Berlin für Materialien und Energie within a bilateral Russian-German Laboratory program. The authors express gratitude to Orekhov A. S. for help with the STEM image simulation. This work was performed using the equipment of the Shared Research Centre FSRC “Crystallography and Photonics” RAS and was supported by the Russian Ministry of Education and Science.Peer Reviewe

Isolation of cubic Si3P4 in the form of nanocrystals

This article describes an approach for synthesizing silicon phosphide nanoparticles with a defective zinc blende structure under mild conditions through thermal annealing of hydrogenated silicon nanoparticles with red phosphorus. The synthesized Si3P4 nanoparticles were analyzed using FTIR, XRD, electron diffraction, EDX, TEM, Raman spectroscopy, X-ray fluorescence spectrometry, and UV–vis spectrophotometry. For the isolated cubic Si3P4 phase, a cell parameter of a = 5.04 Å was determined, and the bandgap was estimated to be equal to 1.25 eV. Because of the nanoscale dimensions of the obtained Si3P4 nanoparticles, the product may exhibit several exceptional properties as a precursor for diffusion doping of wafers and as anode material for Li-ion batteries. A similar method with a hydrogenation step offers the possibility to obtain other compounds, such as silicon selenides, arsenides, and sulfides