Abstract: The crystal structure of the group of optical materials Ln2MeGe4O12, Ln = Eu, Gd, Dy-Lu, Y; Me = Ca, Mn and of the solid solution (Y1-xErx)2CaGe4O12 (x = 0 – 1), promising materials for photonics, has been studied in detail. The crystal structure of all compounds exhibit two alternating layers: one formed by Ln and Me atoms and another by cyclic [Ge4O12]8- anions.

Abstract: The Bi3n+1Ti7Fe3n-3,O9n+11 materials are built of (001)(p) plane parallel perovskite blocks with a thickness of n (Ti,Fe)O-6 octahedra, separated by periodic translational interfaces. The interfaces are based on anatase-like chains of edge -sharing (Ti,Fe)O-6 octahedra. Together with the octahedra of the perovskite blocks, they create S-shaped tunnels stabilized by lone pair Bi3+ cations. In this work, the structure of the n = 4-6 Bi3n+1Ti7Fe3n-3,O9n+11 homologues is analyzed in detail using advanced transmission electron microscopy, powder X-ray diffraction, and Mossbauer spectroscopy. The connectivity of the anatase-like chains to the perovskite blocks results in,a 3ap periodicity along the interfaces, so that they can be located either on top of each other or with shifts of +/- a(p) along [100](p). The ordered arrangement of the interfaces gives rise to orthorhombic Immm and monoclinic A2/m polymorphs with the unit cell parameters a = 3a(p), b = b(p), c = 2(n + 1)c(p) and a = 3a(p), b = b(p), c = 2(n + 1)c(p) – a(p), respectively. While the n = 3 compound is orthorhombic, the monoclinic modification is more favorable in higher homologues. The Bi3n+1Ti7Fe3n-3,O9n+11 structures demonstrate intricate patterns of atomic displacements in the perovskite blocks, which are supported by the stereochemical activity of the Bi3+ cations. These patterns are coupled to the cationic coordination of the oxygen atoms in the (Ti,Fe)O-2 layers at the border of the perovskite blocks. The coupling is strong in the 1/ = 3, 4 homologues, but gradually reduces with the increasing thickness of the perovskite blocks, so that, in the n = 6 compound, the dominant mode of atomic displacements is aligned along the interface planes. The displacements in the adjacent perovskite blocks tend to order antiparallel, resulting in an overall antipolar structure. The Bi3n+1Ti7Fe3n-3,O9n+11 materials demonstrate an unusual diversity of structure defects. The n = 4-6 homologues are robust antiferromagnets below T-N = 135, 220, and 295 K, respectively. They show a high dielectric constant that weakly increases with temperature and is relatively insensitive to the Ti/Fe ratio.

Abstract: Among lithium battery cathode materials, Li1.2Ni0.13Mn0.54Co0.13O2 (LR-NMC) has a high theoretical capacity, but suffers from voltage and capacity fade during cycling. This is partially ascribed to transition metal cation migration, which involves the local transformation of the honeycomb layered structure to spinel-like nano-domains. Determination of the honeycomb layered/spinel phase ratio from powder X-ray diffraction data is hindered by the nanoscale of the functional material and the domains, diverse types of twinning, stacking faults, and the possible presence of the rock salt phase. Determining the phase ratio from transmission electron microscopy imaging can only be done for thin regions near the surfaces of the crystals, and the intense beam that is needed for imaging induces the same transformation to spinel as cycling does. In this article, it is demonstrated that the low electron dose sufficient for electron diffraction allows the collection of data without inducing a phase transformation. Using calculated electron diffraction patterns, we demonstrate that it is possible to determine the volume ratio of the different phases in the particles using a pair-wise comparison of the intensities of the reflections. Using this method, the volume ratio of spinel structure to honeycomb layered structure is determined for a submicron sized crystal from experimental three-dimensional electron diffraction (3D ED) and precession electron diffraction (PED) data. Both twinning and the possible presence of the rock salt phase are taken into account. After 150 charge-discharge cycles, 4% of the volume in LR-NMC particles was transformed irreversibly from the honeycomb layered structure to the spinel structure. The proposed method would be applicable to other multi-phase materials as well.

Abstract: Complex transition-metal oxides exhibit a wide variety of chemical and physical properties which are a strong function the local electronic states of the transition-metal centres, as determined by a combination of metal oxidation state and local coordination environment. Topochemical reduction of the double perovskite oxide, LaSrCoRuO6, using Zr, yields LaSrCoRuO5. This reduced phase contains an ordered array of apex-linked square-based pyramidal Ru3+O5, square-planar Co1+O4 and octahedral Co3+O6 units, consistent with the coordination-geometry driven disproportionation of Co2+. Coordination-geometry driven disproportionation of d(7) transition-metal cations (e.g. Rh2+, Pd3+, Pt3+) is common in complex oxides containing 4d and 5d metals. However, the weak ligand field experienced by a 3d transition-metal such as cobalt leads to the expectation that d(7+) Co2+ should be stable to disproportionation in oxide environments, so the presence of Co1+O4 and Co3+O6 units in LaSrCoRuO5 is surprising. Low-temperature measurements indicate LaSrCoRuO5 adopts a ferromagnetically ordered state below 120 K due to couplings between S=(1)/(2) Ru3+ and S=1 Co1+.

Abstract: Nanocrystalline tin dioxide modified by Pd and Pt clusters or by bimetallic PdPt nanoparticles was synthesized. Distribution of the modifers on the SnO2 surface was studied by high-resolution transmission electron microscopy and energy dispersive X-ray microanalysis with element distribution mapping. It was shown that the Pd/Pt ratio in bimetallic particles varies over a broad range and does not depend on the particle diameter. The effect of platinum metals on the reducibility of nanocrystalline SnO2 by hydrogen was determined. The sensing properties of the resulting materials towards 6.7 ppm CO in air were estimated in situ by electrical conductivity measurements. The sensor response of SnO2 modified with bimetallic PdPt particles was a superposition of the signals of samples with Pt and Pd clusters.

Abstract: The hydrothermal aging stability of 3Y-TZP-xM2O3 (M = La, Nd, Sc) was investigated as a function of 0.02–5 mol% M2O3 dopant content and correlated to the overall phase content, t-ZrO2 lattice parameters, grain size distribution, grain boundary chemistry and ionic conductivity.
The increased aging stability with increasing Sc2O3 content and the optimum content of 0.4–0.6 mol% Nd2O3 or 0.2–0.4 mol% La2O3, resulting in the highest aging resistance, could be directly related to the constituent phases and the lattice parameters of the remaining tetragonal zirconia.
At low M2O3 dopant contents ≤0.4 mol%, the different aging behavior of tetragonal zirconia was attributed to the defect structure of the zirconia grain boundary which was influenced by the dopant cation radius. It was observed that the grain boundary ionic resistivity and the aging resistance followed the same trend: La3+ > Nd3+ > Al3+ > Sc3+, proving that hydrothermal aging is driven by the diffusion of water-derived mobile species through the oxygen vacancies. Accordingly, we elucidated the underlying mechanism by which a larger trivalent cation segregating at the zirconia grain boundary resulted in a higher aging resistance.

Abstract: Factors affecting the structure and orientation of the crystallographic shear (CS) planes in anion-deficient perovskites are investigated using the (Pb1−zSrz)1−xFe1+xO3−y perovskites as a model system. The orientation of the CS planes in the system varies unevenly with z. A comparison of the structures with different CS planes revels that the orientation of the CS planes is governed mainly by the stereochemical activity of the lone-electron-pair cations inside the perovskite blocks.

Abstract: For the development of the photovoltaic industry cheap methods for the synthesis of Cu(In,Ga)Se-2 (CIGSe) based solar cells are required. In this work, CIGSe thin films were obtained by a solution-based method using oxygen-bearing derivatives. With the aimof improving the morphology of the printed CIGSe layers, we investigated two different annealing conditions of the precursor layer, consisting of (1) a direct selenization step (reference process), and (2) a pre-treatment thermal step prior to the selenization. We showed that the use of an Air/H2S burn-out step prior to the selenization step increases the CIGSe grain size and reduces the carbon content. However, it leads to the reduction of the solar cell efficiency from 4.5% in the reference sample down to 0.5% in the annealed sample. Detailed transmission electron microscopy analysis, including high angle annular dark field scanning transmission electron microscopy and energy dispersive X-ray mapping, was applied to characterize the microstructure of the film and to determine the relationship between microstructure and the solar cell performance. We demonstrated that the relatively low efficiency of the reference solar cells is related not only to the nanosize of the CIGSe grains and presence of the pores in the CIGSe layer, but also to the high amount of secondary phases, namely, In/Ga oxide (or hydroxide) amorphous matter, residuals of organicmatter (carbon), and copper sulfide that is formed at the CIGSe/MoSe2 interface. The annealing in H2S during the burn-out step leads to the formation of the copper sulfide at all grain boundaries and surfaces in the CIGSe layer, which results in the noticeably efficiency drop. (C) 2015 Elsevier B.V. All rights reserved.

Abstract: Nanocomposites In2O3/Ag obtained by ultraviolet (UV) photoreduction and impregnation methods were studied as materials for CO sensors operating in the temperature range 25-250 degrees C. Nanocrystalline In2O3 and In2O3/Ag nanocomposites were characterized by X-ray diffraction (XRD), single-point Brunauer-Emmet-Teller (BET) method, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and high angle annular dark field scanning transmission electron microscopy (HAADF-STEM) with energy dispersive X-ray (EDX) mapping. The active surface sites were investigated using Fourier-transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), electron paramagnetic resonance (EPR) spectroscopy and thermo-programmed reduction with hydrogen (TPR-H-2) method. Sensor measurements in the presence of 15 ppm CO demonstrated that UV treatment leads to a complete loss of In2O3 sensor sensitivity, while In2O3/Ag-UV nanocomposite synthesized by UV photoreduction demonstrates an increased sensor signal to CO at T < 200 degrees C. The observed high sensor response of the In2O3/Ag-UV nanocomposite at room temperature may be due to the realization of an additional mechanism of CO oxidation with participation of surface hydroxyl groups associated via hydrogen bonds.

Abstract: <script type='text/javascript'>document.write(unpmarked('gamma-Fe and related alloys are model systems of the coupling between structure and magnetism in solids. Since different electronic states (with different volumes and magnetic ordering states) are closely spaced in energy, small perturbations can alter which one is the actual ground state. Here, we demonstrate that the ferromagnetic state of gamma-Fe nanoparticles is associated with a tetragonal distortion of the fcc structure. Combining a wide range of complementary experimental techniques, including low-temperature Mossbauer spectroscopy, advanced transmission electron microscopy, and synchrotron radiation techniques, we unambiguously identify the tetragonally distorted ferromagnetic ground state, with lattice parameters a = 3.76(2) angstrom and c = 3.50(2) angstrom, and a magnetic moment of 2.45(5) mu(B) per Fe atom. Our findings indicate that the ferromagnetic order in nanostructured gamma-Fe is generally associated with a tetragonal distortion. This observation motivates a theoretical reassessment of the electronic structure of gamma-Fe taking tetragonal distortion into account.'));