Alexandra E. Maegli

The influence of defects formed by Ca excess and thermal post-treatments on the persistent luminescence of CaTiO_3:Pr

Red emitting CaTiO3:Pr phosphors with a nominal composition of Ca0.998+xPr0.002TiO3+δ (0.02≤x≤0.04) were prepared by solid state reactions with different thermal post treatments and characterized by X-ray diffraction, transmission electron microscopy and photoluminescence. The Ca excess exhibited complete solubility up to 4% in the samples treated at 1400 °C but segregation in the form of Ruddlesden-Popper phases (Ca3Ti2O7 - Ca4Ti3O10) was observed in samples prepared at 1500 °C. The increase in temperature for stoichiometric samples showed a monotonic increase of decay time due to the reduction of non-radiative recombination defects. It was found that the Ca excess favored the formation of oxygen vacancies which are known to act as trap. In the samples treated at 1400 °C, 3% of Ca excess showed to be the best concentration to increase the decay time of persistent luminescence. For the samples treated at 1500 °C, the segregation of Ruddlesden-Popper phases left a constant amount of Ca soluble in all the CaTiO3 samples. This constant concentration of Ca caused the same density of defects and, consequently, the same decay time in all samples.

Structure and thermoelectric properties of EuTi(O,N)3 ± δ

After partial substitution of nitrogen for oxygen in EuTiO3, the crystal structure, thermoelectric properties, morphology, and electronic structure of the products were analyzed and compared with pristine EuTiO3. The space group of EuTi(O,N)3 ± δ was orthorhombic Pnma due to the tilt and rotation of the anion octahedra, compared to cubic Pm3¯m of EuTiO3 (at room temperature). The thermoelectric properties of oxynitride polycrystalline bodies sintered in three different ways were investigated in the temperature range of 300 K < T < 950 K. The Seebeck coefficients (S) of the oxynitrides were lower compared with the oxide, and the electrical resistivities (ρ) were increased about one order of magnitude. The activation energies (EA) indicated a larger band gap of EuTi(O,N)3 ± δ when compared to the pristine EuTiO3 (∼1.3 eV compared to 0.98 eV). A morphological characterization by transmission electron microscopy and scanning electron microscopy illustrated intrinsic nanopores within the individual particles a...

Improved photoluminescence and afterglow of CaTiO 3 :Pr 3+ by ammonia treatment

The phosphor CaTiO3:Pr3+ was synthesized via a solid-state reaction in combination with a subsequent annealing under flowing NH3. Comparatively large off-center displacements of Ti in the TiO6 octahedra were confirmed for as-synthesized CaTiO3:Pr3 by XANES. Raman spectroscopy showed that the local crystal structure becomes highly symmetric when the powders are ammonolyzed at 400 °C. Rietveld refinement of powder X-ray diffraction data revealed that the samples ammonolyzed at 400 °C have the smallest lattice strain and at the same time the largest average Ti-O-Ti angles were obtained. The samples ammonolyzed at 400 °C also showed the smallest mass loss during the thermal re-oxidation in thermogravimetric analysis (TGA). Enhanced photolumincescence brightness and an improved decay curve as well as the highest reflectance were obtained for the samples ammonolyzed at 400 °C. The improved photoluminescence and afterglow by NH3 treatment are explained as a result of the reduced concentration of oxygen excesses with simultaneous relaxation of the lattice strain.

Structure stability of Li x H y V 3 O 8 exposed to water-vapour

Chemically lithiated Li x H y V 3 O 8 was prepared as the starting material in this study owing to its interesting properties for lithium-ion intercalation and further application in the positive electrode of lithium-ion batteries. The hydrophilic character of the synthesised compound was evaluated because even ppm water level inside batteries containing electrolytes with fluorinated salts like LiPF 6 can dramatically influence the battery stability. The structural stability of the lithiated vanadate after exposure to water-vapour was evaluated ex situ by XRD, TGA and TEM. TGA showed that at least 4 wt.% of water can be incorporated into the material. Water intercalates in the vanadate lattice filling the particles from the outer shell towards the bulk. Prolonged exposure to water-vapour saturated atmosphere leads to irreversible exfoliation of the crystal structure. Weakly bonded intercalated water can be removed without any damage to the crystal structure by an annealing step at 200oC for 2 h in air.

The Influence of the Ammonolysis Temperature on the Photocatalytic Activity of β-TaON

Phase-pure tantalum oxynitride (β-TaON) powders were synthesized by thermal ammonolysis of Ta2O5 powders. X-ray diffraction revealed an enlargement of the unit cell and an increase of the crystallite size with increasing ammonolysis temperature. Scanning electron microscopy showed reduced particle sizes for β-TaON synthesized at 800 and compared to the precursor oxide. With increasing nitridation temperature the Brunauer-Emmett-Teller surface area was reduced and the nitrogen content increased. UV-Vis spectroscopy showed a bandgap energy of 2.6–2.4 eV. The highest oxygen evolution rate of 220 μmol·g−1·h−1 was achieved for β-TaON synthesized at . The factors determining the photocatalytic activity of β-TaON powders were found to be the specific surface area and defects in the β-TaON.