• Photocatalytic CO2 reduction by Cr-substituted Ba2(In2-xCrx )O5 ·(H2O)δ (0.04 ≤ x ≤ 0.60)
    S. Yoon, M. Gaul, S. Sharma, K. Son, H. Hagemann, D. Ziegenbalg, U. Schwingenschlogl, M. Widenmeyer and A. Weidenkaff
    Solid State Sciences, in press (2018)
    DOI:10.1016/j.solidstatesciences.2018.02.005 | Abstract
Cr-substituted polycrystalline Ba2(In2-xCrx)O5·(H2O)δ powders (0.04 ≤ x ≤ 0.60) were synthesized by solid state reaction to investigate the relation of crystal structure, thermochemical, magnetic, and optical properties. The Cr-substitution results in an unit cell expansion and formation of the higher-symmetric tetragonal phase together with increased oxygen and hydrogen contents. Magnetic property measurements reveal that the diamagnetic pristine Ba2In2O5·(H2O)δ becomes magnetically ordered upon Cr-substitution. By UV–vis spectroscopy a gradual shift of the absorption-edge energy to lower values was observed. Numerical calculations showed that the observed bandgap narrowing was ascribed to the Cr induced states near the Fermi level. The correlation between the changes of crystal chemistry, magnetic, and optical properties of Cr-substituted Ba2(In2-xCrx)O5·(H2O)δ can be explained by the replacement of In by Cr. Consequently, an enhanced photocatalytic CO2 reduction activity was observed with increasing Cr substitution, compatible with the state-of-the-art high surface area TiO2 photocatalyst (P-25).
 
Cr-substituted and pristine Ba2In2O5·(H2O)x powders were synthesized by solid state reaction. The influence of Cr-substitution on the crystal structure, chemical composition, magnetic and optical properties were investigated. Powder X-ray diffraction (XRD), elemental analysis and TGA-MS reveal that with substitution of In for Cr, the unit cell volume and the unit cell parameter b increase together with the oxygen and hydrogen content. Magnetic property measurements indicate that Ba2In2O5·(H2O)x is diamagnetic in the temperature range of 2 K < T < 300 K becoming ferromagnetic upon Cr-substitution. In the UV–vis spectra of the Cr-substituted sample a distinctive shift of the absorption-edge energy from 430 to 690 nm was observed corresponding to a bandgap narrowing from 2.88 to 1.80 eV. The replacement of tetrahedral InO4 units by octahedral CrO6 units was found to be the main factor for the drastic change of the magnetic and optical properties.
  
SrAl2O4 doped with europium and dysprosium is a powerful and widely used afterglow material. Within this material strontium is found in two crystallographic different sites. Due to the similar ion radii and same charge, Eu2+-ions can occupy both sites, resulting in two different Eu2+-ions, one emitting in the blue and one in the green spectral range. The blue emission is thermally quenched at room temperature. In this paper we investigate the energy transfer between different Eu ions depending on the concentration and temperature using two different approaches: lifetime measurements and integrated intensity. We find an activation energy for the thermal quenching of the blue emission of 0.195 ± 0.023 eV and a critical radius for the energy transfer of 3.0 ± 0.5 nm. This results can help in designing better afterglow materials due to the fact that with energy transfer parts of the lost emission in the blue region at room temperature can be converted to the green site.
The persistent phosphorescence and thermoluminescence of SrAl2O4:Eu2+:Dy3+ is reported for a variety of different excitation wavelengths and excitation temperatures, to provide new insights in the mechanism of the trapping and detrapping. These measurements reveal that the trapping is strongly dependent on the wavelength and temperature. First, with increasing loading temperature, the thermoluminescence peak shifts to lower temperatures which corresponds to a change of trap population. Secondly, the integrated thermoluminescent intensity increases with increasing loading temperature. All wavelength and temperature dependent experiments indicate that the loading of the traps is a thermally activated processes. Utilizing different wavelengths for loading, this effect can be enhanced or reduced. Furthermore excitation with UV-B-light reveals a tendency for detrapping the phosphor, reducing the resulting thermoluminescent intensity and changing the population of the traps.
Persistent luminescence of SrAl2O4:Eu2+ has attracted considerable attention due to their high initial brightness, long-lasting time and excellent thermal stability. Here the influence of boric acid on the persistent luminescence and thermal oxidation resistance of SrAl2O4:Eu2+ was investigated in detail. Crystal structural analysis and scanning electron microscopy revealed that with the addition of boron, the unit cell volume decreased and the morphology of the particles became more irregular with sharp edges. Thermogravimetric analysis showed better thermal oxidation resistance accompanied by a change in oxygen vacancy concentration when boron acid is used. Photoluminescence spectra and afterglow decay curves confirm an improved afterglow performance for boron-added SrAl2O4:Eu2+. Thermoluminesence allowed monitoring the changes in the trap states due to the presence of B. Our results imply that the substantial improvement of afterglow performance and the thermal stability in SrAl2O4:Eu2+ can be attributed to the incorporation of boron into the aluminate network.
  • Improved persistent luminescence of CaTiO3:Pr by fluorine substitution and thermochemical treatment
    S. Yoon, E.H. Otal, A.E. Maegli, L. Karvonen, S.K. Matam, S.G. Ebbinghaus, B. Walfort, H. Hagemann, S. Pokrant and A. Weidenkaff
    Journal of Alloys and Compounds, 613 (2014), p338-343
    DOI:10.1016/j.jallcom.2014.06.041 | unige:38546 | Abstract | Article HTML | Article PDF
Fluorine-substituted CaTiO3:Pr phosphors were prepared by a solid-state reaction. Rietveld refinements of powder X-ray diffraction patterns revealed that increasing fluorine-substitution leads to the gradual shrinkage of the unit-cell. Enhanced afterglow intensities were observed with fluorine-substitution. Furthermore, the effect of annealing atmosphere was investigated by thermochemical treatment in different atmospheres (Ar, air and NH3). UV-Vis diffuse reflectance spectra and photoluminescence excitation spectra revealed that Pr4+ in the pristine CaTi(O,F)3:Pr phosphor was partially reduced to Pr3+ under NH3 flow leading to an intensity improvement of ca. 450% compared to CaTiO3:Pr. The substantial improvement of afterglow intensity by fluorine substitution and annealing in NH3 is considered to be connected with the generation of oxygen vacancies and the partial reduction of Pr4+ to Pr3+.
  • Improved photoluminescence and afterglow of CaTiO3:Pr3+ by ammonia treatment
    S. Yoon, E.H. Otal, A.E. Maegli, L. Karvonen, S.K. Matam, S. Riegg, S.G. Ebbinghaus, J.C. Fallas, H. Hagemann, B. Walfort, S. Pokrant and A. Weidenkaff
    Optical Materials Express, 3 (2) (2013), p248-259
    DOI:10.1364/OME.3.000248 | unige:26402 | Abstract | Article HTML | Article PDF
 
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.
  
  • The influence of defects formed by Ca excess and thermal post-treatments on the persistent luminescence of CaTiO3:Pr
    E.H. Otal, A.E. Maegli, N. Vogel-Schäuble, B. Walfort, H. Hagemann, S. Yoon, A. Zeller and A. Weidenkaff
    Optical Materials Express, 2 (4) (2012), p405-412
    DOI:10.1364/OME.2.000405 | unige:18791 | Abstract | Article HTML | Article PDF
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.

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Last update Friday March 02 2018