Abstract: Three-dimensional topological insulators are exotic materials with unique properties. Tetradymite type binary chalcogenides of bismuth and antimony, as well as their mixed crystals, belong to prototypical TIs. Potential device applications of these materials require in-depth knowledge of their stability in the ambient atmosphere and other media maintained during their processing. Here we investigated the reactivity of mixed crystals with anion substitution, Bi-2(Se1-xTex)(3) and Sb2(Se1-xTex)(3), towards molecular oxygen using both in situ and ex situ X-ray photoelectron spectroscopy. The results indicate that, in contrast to cation substitution, partial substitution of tellurium by selenium atoms leads to anomalously high surface reactivity, which even exceeds that of the most reactive binary constituent. We attribute this effect to anion ordering that essentially modifies the bond geometry, especially the respective bond angles as modeled by DFT.

Abstract: To obtain a nanocrystalline SnO2 matrix and mono- and bimetallic nanocomposites SnO2/Pd, SnO2/Pt, and SnO2/PtPd, a flame spray pyrolysis with subsequent impregnation was used. The materials were characterized using X-ray diffraction (XRD), a single-point BET method, transmission electron microscopy (TEM), and high angle annular dark field scanning transmission electron microscopy (HAADF-STEM) with energy dispersive X-ray (EDX) mapping. The electronic state of the metals in mono- and bimetallic clusters was determined using X-ray photoelectron spectroscopy (XPS). The active surface sites were investigated using the Fourier Transform infrared spectroscopy (FTIR) and thermo-programmed reduction with hydrogen (TPR-H-2) methods. The sensor response of blank SnO2 and nanocomposites had a carbon monoxide (CO) level of 6.7 ppm and was determined in the temperature range 60-300 degrees C in dry (Relative Humidity (RH) = 0%) and humid (RH = 20%) air. The sensor properties of the mono- and bimetallic nanocomposites were analyzed on the basis of information on the electronic state, the distribution of modifiers in SnO2 matrix, and active surface centers. For SnO2/PtPd, the combined effect of the modifiers on the electrophysical properties of SnO2 explained the inversion of sensor response from n- to p-types observed in dry conditions.

Abstract: The behavior of ternary mixed crystals or solid solutions and its correlation with the properties of their binary constituents is of fundamental interest. Due to their unique potential for application in future information technology, mixed crystals of topological insulators with the spin-locked, gapless states on their surfaces attract huge attention of physicists, chemists and material scientists. (Bi1-xSbx)(2)Te-3 solid solutions are among the best candidates for spintronic applications since the bulk carrier concentration can be tuned by varying x to obtain truly bulk-insulating samples, where the topological surface states largely contribute to the transport and the realization of the surface quantum Hall effect. As this ternary compound will be evidently used in the form of thin-film devices its chemical stability is an important practical issue. Based on the atomic resolution HAADF-TEM and EDX data together with the XPS results obtained both ex situ and in situ, we propose an atomistic picture of the mixed crystal reactivity compared to that of its binary constituents. We find that the surface reactivity is determined by the probability of oxygen attack on the Te-Sb bonds, which is directly proportional to the number of Te atoms bonded to at least one Sb atom. The oxidation mechanism includes formation of an amorphous antimony oxide at the very surface due to Sb diffusion from the first two quintuple layers, electron tunneling from the Fermi level of the crystal to oxygen, oxygen ion diffusion to the crystal, and finally, slow Te oxidation to the +4 oxidation state. The oxide layer thickness is limited by the electron transport, and the overall process resembles the Cabrera-Mott mechanism in metals. These observations are critical not only for current understanding of the chemical reactivity of complex crystals, but also to improve the performance of future spintronic devices based on topological materials.

Abstract: Nanocomposites CoOx/SnO2 based on tin oxide powders with different crystallinity have been prepared by wet chemical synthesis and characterized in detail by ICP-MS, XPS, EPR, XRD, HAADF-STEM imaging and EDX-STEM mapping. It was shown that cobalt is distributed differently between the bulk and surface of SnO2 nanocrystals, which depends on the crystallinity of the SnO2 matrix. The measurements of gas sensor properties have been carried out during exposure to CO (10 ppm), and H2S (2 ppm) in dry air. The decrease of sensor signal toward CO was attributed to high catalytic activity of Co3O4 leading to oxidation of carbon monoxide entirely on the surface of catalyst particles. The formation of a p-CoOx/n-SnO2 heterojunction results in high sensitivity of nanocomposites in H2S detection. The conductance significantly changed in the presence of H2S, which was attributed to the formation of metallic cobalt sulfide and removal of the p – n junction.