Thermal evolution of the crystal structure and phase transitions of KNbO3.

The thermal evolution of the crystal structure and phase transitions of KNbO3 were investigated by high-temperature powder X-ray diffraction and Rietveld refinement of the diffraction data. Two phase transitions from orthorhombic (Amm2) to tetragonal (P4mm) and from tetragonal to cubic ( Pm3¯m ) were confirmed, both on heating and cooling. Both phase transitions are first order based on the observed hysteresis. The mixed displacive and order-disorder nature of the tetragonal to cubic transition is argued based on symmetry and apparent divergence of the atomic positions from pseudo-cubic values. The transition between the orthorhombic and tetragonal phase shows no temperature-dependence for atomic positions and only thermal expansion of the unit cell parameters and is thus discussed in relation to a lattice dynamical instability.

Electrical conductivity and thermopower of (1 - x) BiFeO(3) - xBi(0.5)K(0.5)TiO3 (x = 0.1, 0.2) ceramics near the ferroelectric to paraelectric phase transition.

Ferroelectric BiFeO3 has attractive properties such as high strain and polarization, but a wide range of applications of bulk BiFeO3 are hindered due to high leakage currents and a high coercive electric field. Here, we report on the thermal behaviour of the electrical conductivity and thermopower of BiFeO3 substituted with 10 and 20 mol% Bi0.5K0.5TiO3. A change from p-type to n-type conductivity in these semi-conducting materials was demonstrated by the change in the sign of the Seebeck coefficient and the change in the slope of the isothermal conductivity versus partial pressure of O. A minimum in the isothermal conductivity was observed at ∼10(-2) bar O2 partial pressure for both solid solutions. The strong dependence of the conductivity on the partial pressure of O2 was rationalized by a point defect model describing qualitatively the conductivity involving oxidation/reduction of Fe(3+), the dominating oxidation state of Fe in stoichiometric BiFeO3. The ferroelectric to paraelectric phase transition of 80 and 90 mol% BiFeO3 was observed at 648 ± 15 and 723 ± 15 °C respectively by differential thermal analysis and confirmed by dielectric spectroscopy and high temperature powder X-ray diffraction.

Optical properties of single diatom frustules revealed by confocal microspectroscopy.

Optical properties of single diatom frustule valves from two different Coscinodiscus species (C. wailesii and C. centralis) are studied by transmission confocal hyperspectral imaging and numerical calculations. Light convergence, concentration, and trapping effects are observed and depend on both the wavelength and the valve orientation. These effects seem to occur independently of the incident light angle. From our results, a wavelength-dependent multifocal lens behavior can be explained by light diffraction related to the radial symmetry of the multiscaled 3D nanostructure.

Solid solubility of rare earth elements (Nd, Eu, Tb) in In2-xSnxO3 - effect on electrical conductivity and optical properties.

Wide band-gap semiconductors doped with luminescent rare earth elements (REEs) have attracted recent interest due to their unique optical properties. Here we report on the synthesis of the transparent conducting oxides (TCOs) indium oxide and indium tin oxide (ITO) doped with neodymium, europium and terbium. The solid solubility in the systems was investigated and isothermal phase diagrams at 1400 °C were proposed. The solubility of the REEs in In2O3 is mainly determined by the size of the rare earth dopant, while in ITO the solid solubility was reduced due to a strong tendency of the tin and REE co-dopants to form a pyrochlore phase. The effect of the REE-doping on the conductivity of the host was determined and optical activity of the REE dopants were investigated in selected host materials. The conductivity of sintered materials of REE-doped In2O3 was significantly reduced, even at small doping concentrations, due to a decrease in carrier mobility. The same decrease in mobility was not observed in thin films of the material processed at lower temperatures. Strong emissions at around 611 nm were observed for Eu-doped In2O3, demonstrating the possibility of obtaining photoluminescence in a TCO host, while no emissions was observed for Nd- and Tb-doping.

Octoxy capped Si nanoparticles synthesized by homogeneous reduction of SiCl4 with crown ether alkalide.

Blue-green luminescent octoxy capped Si nanoparticles were synthesized via homogeneous reduction of SiCl4 with the crown ether alkalide K(+)(15-crown-5)2K(-) in tetrahydrofuran. The Si nanoparticles were characterized with respect to size, crystal structure, morphology, surface termination, optical properties and stability. Si diamond structure nanoparticles with narrow size distributions, and average diameters ranging from 3 to 7 nm were obtained. A finite-size effect on the lattice dimensions was observed, in the form of an expansion of the [220] lattice planes of smaller Si nanoparticles. The concentration of SiCl4 was found to be the most important parameter governing the particle size and size distribution. The octoxy capped particles were stable under an ambient atmosphere for at least one month, but exposure to water made them prone to oxidation. An average radiative recombination lifetime of 8.8 ns was measured for the blue-green luminescence. The luminescence appears to originate from surface defects, rather than from quantum confinement.

Melting of Bi sublattice in nanosized BiFeO3 Perovskite by resonant X-ray diffraction.

Free-standing BiFeO3 perovskite particles with a size ranging from polycrystalline bulk down to 5 nm have been studied by high-energy resonant (Bi K edge) x-ray diffraction coupled to differential atomic pair distribution function analysis. Nanosized BiFeO3 particles are found to exhibit extra, i.e., beyond the usual thermal, structural disorder that increases progressively with diminishing their size. In particles of size smaller than approximately 18 nm the disorder destroys the structural coherence of the Bi sublattice and disturbs that of the Fe-based sublattice in the perovskite structure, substantially affecting the magnetoelectric properties it carries. The new structural information helps better understand the unusual behavior of perovskites structured at the nanoscale.