Ternary thallium chalcogenides of the formula Tl4MQ4, where M = Zr and Hf and Q = S, Se, and Te were synthesized and characterized. Our X-ray diffraction studies on suitable single crystals reveal that the sulphides and selenides are isostructural, with monoclinic space group P, whereas the corresponding tellurides crystallize in the rhombohedral crystal system (R). The structures of the sulphides and selenides are comprised of zigzag chains of edge-sharing MQ6 octahedra, whereas the MTe6 octahedra are interconnected via common faces to form linear trimeric units. In all cases, the atoms adopt common oxidation states, namely Tl+, M4+, and Q2–. The electronic structure calculations using the linear muffin tin orbital (LMTO) method predicted band gaps of 1.7 eV, 1.3 eV and 0.3 eV for the sulphides, selenides and tellurides, respectively, implying sulphides and selenides are large band gap materials, and the tellurides narrow gap semiconductors. Their electronic transport properties are also evaluated with respect to the thermoelectric energy conversion.

We have investigated electronic deep levels in free-standing n-GaN substrates grown by hydride vapor phase epitaxy (HVPE), by means of a steady-state photo-capacitance spectroscopy technique, using transparent conductive polyaniline Schottky contacts. Two specific deep levels located at ~1.7 and ~3.1 eV below the conduction band were revealed to be significantly reduced compared to those in n-GaN layers grown by metal-organic chemical vapor deposition. This difference between them is probably due to extremely low concentrations of threading dislocations and residual C impurities in the HVPE-grown n-GaN substrates.

We have investigated a correlation between electronic deep levels and current collapses in AlGaN/GaN hetero-structures by capacitance-voltage and photo-capacitance spectroscopy techniques, using Schottky barrier diodes. Three specific deep levels located at ~2.07, ~2.80, ~3.23eV below the conduction band were found to be significantly enhanced for the severe current collapse. These levels probably originate in Ga vacancies and residual C impurities and are probably responsible for the current collapses of the AlGaN/GaN hetero-structures.

By carefully manipulating and controlling the growth conditions, Ruthenium (Ru) and ruthenium oxide (RuO2) two-dimensional (2-D) nanostructure were self-assembled into a stack of plates on indium tin oxide coated glass substrate. The nanoplates were grown in a horizontal hot-wall metalorganic chemical vapor deposition (MOCVD) from ruthenocene. Each nanoplate has a thickness in the range of 25 - 60 nm and the average area is 1000 x 300 nm2. Each stack of nanoplates is approximately 1.2 m in height. A continuous layer of Ru and RuO2 thin film, which may serve as the growth template, is observed on the bottom of the nanoplate stacks. Field-emission scanning electron microscopy reveals that each stack of nanoplates was grown vertically aligned on the substrate and exhibited elongated shape. Structural properties which were examined by X-ray diffraction show that the nanoplates are polycrystalline.

Properties of hydrogenated icosahedral aluminum clusters were investigated using density functional theory in comparison with those of aluminum bulk systems. Two surface models simulating f.c.c. and icosahedral (111) surfaces were introduced. Results show that the H atom interacts weakly with surface of clusters when the cluster size is increased. The migration energy of H atom between neighboring T and O sites becomes smaller for icosahedral subsurface than for either bulk material or the f.c.c. subsurface. The results indicate that the icosahedral surface is more favored for H atom to adsorp than f.c.c. surface, the icosahedral surface increases the migration barriers of H atom from the surface to the subsurface.

SrAl4O7 (SA2) phosphor powders were synthesized by using a modified Pechini process. Varying amounts of boron was incorporated into the SA2 lattice to investigate the effects on crystal structure and optical properties. X-ray spectra showed that boron addition enhances phase purity of the powder at a calcination temperature of 1000 °C, whereas the formation of a new S4A7 phase was induced when a calcination temperature of 1100 °C was used. The afterglow duration was extended to longer than 5 hours when boron was present in 4-11 mol%. To elucidate the enhanced optical properties, interband trap characteristics were studied by thermoluminescence and photoluminescence.

In this work, the one dimensional (1D) titanate nanotubes (TNT)/nanowires (TNW), bulk titanate micro-particles (TMP), and three dimensional (3D) titanate microsphere particles (TMS) with high specific surface area were synthesized via different approaches. The chemical composition and structure of these products have been characterized by field emission scanning electron microscopy (FESEM), transmission electron microscope (TEM) study and Raman scattering spectroscopy. The as-prepared TMS shows excellent adsorption performance compared with TMP, TNW and TNT when methylene blue (MB) and PbII ions are used as representative organic and inorganic pollutants.

We present a first principles thermodynamic study of O ad-atom and vacancy formation on the AO- and BO2-terminated (001) surfaces of the PbTiO3 (PTO) and LaMnO3 (LMO) cubic perovskites. Our results show that, owing to the highly energetically unfavorable nature of O vacancy formation on these surfaces, O vacancies appear only at high temperatures and practically irrelevant low pressures on the (T, p) surface phase diagram. In contrast, effortless formation of O ad-atoms on the surfaces is encountered at practically achievable pressures and temperatures. Above room temperature and close to atmospheric pressures, we predict clean PbO and TiO2-terminated (001) PTO surfaces as the stable surface phases while partially or fully O ad-atom covered surfaces are found to be more stable for LMO. These results are consistent with the observation that LMO is far more active towards oxidation catalysis than PTO.

During a two-step sintering practice, important factors such as final grain sizes and residual pore status can be controlled through adjusting the first and second step sintering temperatures and durations. Moreover, the sintering temperatures (both the first and the second step) can be several hundred degrees lower than those in a traditional sintering process to obtain fully dense ceramics. Therefore, it is a potentially cost-effective preparation procedure for ceramics with fine grains. In this work, we successfully demonstrated the synthesis of aggregate-free sesquioxide nanometer-sized powders with a narrow size distribution through a modified chemical co-precipitation process. Subsequently, ytterbium-doped Lu2O3 ceramics of near full density were obtained through a two-step sintering process.

Mesoporous cobalt oxide-tungstophosphoric acid composite frameworks have been synthesized by structure replication from cubic mesoporous KIT-6 silica. The products possess a regular structure with uniform wall thickness (~7 nm) and large internal BET surface area (~87-141 m2/g). The pore walls of these materials consist of nanocrystalline Co3O4 and 12-tungstophosphoric acid (HPW) components with different HPW content, i.e. 6, 15 and 36 wt. %. Total X-ray scattering analysis and UV/vis spectroscopy confirmed the Keggin structure of HPW into the mesoporous frameworks. Preliminary catalytic experiments found that Co3O4-HPW composites exhibited a remarkable activity in the direct decomposition of nitrous oxide into N2 and O2.

It is commonly believed that the parent compounds of high-Tc cupratres are, universally, charge transfer insulators and triggered by Mott physics. In our experiments using metal-organic decomposition (MOD), however, accumulating evidences show that the parent compounds of “electron-doped” superconductors, RE2-xCexCuO4 [RE = rare earth ion] with x = 0, are not Mott insulators but superconductors [1-5]. They have a Tc of 30 K and crystallize in the Nd2CuO4 (T’) structure. Most likely, the sharp contradiction between our results and commonly achieved data originates from the complicated oxygen chemistry in these materials. The as-synthesized specimens contain a fair amount of impurity interstitial oxygen. Throughout the reduction process it is required to remove exclusively impurity oxygen while preserving regular oxygen site occupied in order to obtain superconductivity. With decreasing x the constraints of the reduction process are getting more tight. In this study, we systematically investigated the post-annealing process using MBE-grown T’-Pr2CuO4 films. The MBE films were reduced ex-situ in a tubular furnace following a specially designed 2-step process, as in the case of MOD films. The films were annealed at Ta = 700 - 850°C in a reducing atmosphere (PO2 = 2 x 10−5 − 2 x 10−3 atm) and finally reduced at a lower temperature Tred = 450 – 700°C under vacuum (< 10−4 Torr). The film properties systematically changed with Ta, PO2, and Tred. The optimized Tred varies from 475°C to 650°C mainly depending on Ta, since the microstructure and grain size of the films are determined by Ta. Optimal superconducting properties are Tc of 26 K, while ρ(300 K) = 250 μΩcm, and RRR ~ 10. We believe the combination of thin-film synthesis and specially designed post-reduction process enabled us to obtain nearly intact CuO2 planes. Samples prepared by above-mentioned method unveiled the intrinsic properties of the parent compounds, which are not triggered by Mott physics. This result also agrees with the recent calculation result indicating the parent compounds with T’ structure are not charge transfer insulators [6-8].

In the Bi2O3-MO-P2O5 diagram, on the basis of previous compounds based on 2D-ribbon like units, we have predicted and prepared the infinite term. It contains [Bi2O2]2+ planes arranged within a never-observed crystallographic form. In this series, the ribbons-like units are polycations built on the linkage of n O(Bi,M)4 tetrahedra along their width and infinite in a perpendicular dimension. Hence, this novel form completes the continuous series of analogue compounds, whose building units now extend from the single chain to the infinite plane, via a number of discrete n values (2,3,4,5,6,7,8,9,10,11). The presented materials of formulae Bi4MP2O12 (M= Zn and Mg) roughly show the same crystal structure. However different arrangements of the groups located between the [Bi2O2]2+ planes are at the origin of a complex superstructure in the case of the zinc compounds.

Locating cobalt promoters on catalytically MoS2 structures is a challenging task to achieve; this is due to the size on those MoS2 nanostructures. Previous reports in the literature indicate that specific locations for Co in MoS2 slabs are (1010)-plane creating either a sulfur-Co or Molybdenum-Co termination edge, due to lower energy required for the permutation Mo, S and Co to occur. We present results obtained from Density Functional Theory study done on the interface between MoS2 and Co9S8 crystal structures; the interface show an interesting thiocubane cluster and it is suspected to be the responsible for Mo-S-Co bonding to exist, along with HDS reaction. In order to understand electronic properties on thiocubane Density of States and Mulliken Population Analysis calculations were implemented using Cambridge Serial Total Energy Package (CASTEP). Results indicate a strong electron donation from Co to Mo through intermediate sulfur atom bonded to both metals while an enhanced metallic character is also found.

The mixed-conducting perovskite oxide Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF), given its outstanding oxygen ionic and electronic transport properties, is considered a promising material composition for oxygen transport membranes (OTM) operated at high temperatures.

Its long-term stability under operating conditions is, however, still an important issue. Although the incompatibility of BSCF with CO2-containing atmospheres can be avoided by appropriate means (oxyfuel processes in the absence of carbon dioxide), the thermal as well as the chemical stability of BSCF itself are still under thorough investigation.

This work is focused on the stability of BSCF in the targeted temperature range for OTM applications (700…900 °C) and in atmospheres with low oxygen contents. Previous studies in literature suggest limited chemical stability below oxygen partial pressures pO2 of around 10-6 bar.

By using a coulometric titration method based on a zirconia “oxygen pump” setup, precise control of the oxygen partial pressure pO2 between 1 bar and 10-18 bar was facilitated. Combining electrical measurements on dense ceramic bulk samples performed as a function of pO2 with an XRD phase composition study of single phase BSCF powders subjected to various pO2 treatments, an assessment of the chemical stability of BSCF is facilitated as a function of oxygen partial pressure. It could thus be shown that the pO2 stability limit is considerably lower than previously assumed in literature.

Indium oxide-doped hematite xIn2O3·(1-x)α-Fe2O3 (x = 0.1-0.7) solid solution systems were synthesized using mechanochemical activation. The microstructures, magnetic and thermal properties of the system were dependent on In2O3 molar concentration x and ball milling time. XRD results showed that the completion of In3+ substitution of Fe3+ in hematite lattice occurs after 12 h ball milling for x = 0.1. For x = 0.3, 0.5 and 0.7, the substitutions between In3+ and Fe3+ into hematite and In2O3 lattices occur simultaneously. The lattice parameters of hematite and In2O3 vary as a function of ball milling time. The change in these parameters was due to ions substitution between In3+and Fe3+ and the decrease in grain sizes. Mössbauer spectra of the system with x = 0.3 were fitted with three sextets and two quadrupole-split doublets after milling, representing In3+ substitution of Fe3+ in hematite lattice and Fe3+ substitution of In3+ in two different sites of In2O3 lattice. TGA results showed that the hematite decomposition is enhanced due to the smaller hematite grain size. The crystallization of hematite and In2O3 was suppressed with the drops of enthalpy values due to the stronger solid-solid interactions after ball milling. These caused gradual In3+-Fe3+ substitution in hematite/In2O3 lattices.

The proton conducting perovskites are widely investigated due to their high potential as electrolyte membranes of fuel cells, water steam electrolysers and CO2/syngas converters. Our comprehensive spectroscopic (Raman, IR, neutron), thermogravimetric, elastic and quasi-elastic neutron diffusion as well as conductivity studies performed on Ln/RE- modified zirconate ceramics with controlled densification (90-99% of theoretical density) reveal the important differences between the surface and bulk protonic species. The results clearly show that trivialization of the protonation process complexity can favorite the adsorption of the surface protonic species (hydroxide, hydrocarbonates, etc), prohibit the incorporation of bulk protons, i.e. species responsible for the proton conduction and confuse the understanding of fundamental aspects concerning the proton conductors such as the true nature of conducting species. Our studies reveal that OH- ions are located at the surface of poor densified ceramic and the bulk conducting protons exhibit an ionic, free of covalent-bonded nature.

We present a thermodynamic study of selected transition metals (TM=Cr, Mn, Fe and Co) solubility in ZnO based on the assessment of available thermodynamic data and ab-initio calculations in the respective TM-Zn-O systems. The ab-initio DFT calculations of enthalpies of formation of the involved phases and the energies of substitution defect (TM-Zn) formation were performed using the full-potential APW+lo technique (WIEN2k code) within GGA+U approximation. The calculated energies of mixed oxides and virtual (unstable) TMO end-members of (Zn,TM)O solid solutions are referred to well established thermodynamic data of binary oxides taken from SGTE database. The assessed thermodynamic data are subsequently used for calculation of phase equilibria and construction of the respective pO2-T-x phase (FactSage software). Whereas the solubility of Mn, Fe, and Co in ZnO is found not to exceed 1 mol% at low temperatures (T<900°C), the homogeneity range is substantially enlarged at elevated temperatures (~10 mol% at the eutectic temperature). By contrast, the solubility of Cr turned out to be negligible in the relevant range of T and pO2.

Shape-controlled CaF2 and sapphire crystals were grown by a micro-pulling-down (μ-PD) method and the crystallinities were investigated. By the μ-PD method with crucibles which have special configurations, circular tube-shaped CaF2 crystal, square tube-shaped CaF2 crystal and square tube-shaped sapphire crystal with high transparency were obtained. The grown crystals indicated a single phase of CaF2 and Al2O3 in the XRD measurements. X-ray rocking curve of square tube-shaped sapphire indicated the crystal has no mosaic structure in the crystal and it has high crystallinity comparable to crystals grown by Cz method.

Four new compounds containing vanadosilicate clusters have been synthesized by hydrothermal reactions. The clusters are derived from the [V18O42] Keggin cluster by substitution of V=O caps by Si2O(O,OH)2 species. In Cs9[(V15Si6O46(OH)2Cl)(V2O4)](H2O)6.2, 1, the [V15Si6O46(OH)2] cluster shells are covalently interconnected by VO4 tetrahedra to form an infinite layer. In ((CH3)4N)4[V15Si6O42(OH)6(H2O)](H2O)20, 2, and ((CH3)4N)4(V(H2O)6)2/3 [V15Si6O42(OH)6 (H2O)](H2O), 3, separated [V15Si6O42(OH)6] cluster shells are interlinked by hydrogen bonds to form frameworks with wide channel systems. The separated cluster shell in ((CH3)4N)4((CH3)2NH2)((CH3)2NH) [V14Si8O42(OH)8(HCO2)] (H2O)4.7, 4, has four Si2O(OH)2 species in a tetrahedral configuration. The 2D structure of 1 and 0D structures of 2-4 complement the known 1D and 3D structures formed from such vanadosilicate shells.