• Energy Research

The possibility of band gap engineering (BGE) in RAlO3 (R = Y, La, Gd, Yb, Lu) perovskites in the context of trap depths of intrinsic point defects was investigated comprehensively using experimental and theoretical approaches. The optical band gap of the materials, E g, was determined via both the absorption measurements in the VUV spectral range and the spectra of recombination luminescence excitation by synchrotron radiation. The experimentally observed effect of E g reduction from ∼8.5 to ∼5.5 eV in RAlO3 perovskites with increasing R3+ ionic radius was confirmed by the DFT electronic structure calculations performed for RMIIIO3 crystals (R = Lu, Y, La; MIII = Al, Ga, In). The possibility of BGE was also proved by the analysis of thermally stimulated luminescence (TSL) measured above room temperature for the far-red emitting (Y/Gd/La)AlO3:Mn4+ phosphors, which confirmed decreasing of the trap depths in the cation sequence Y → Gd → La. Calculations of the trap depths performed within the super cell approach for a number of intrinsic point defects and their complexes allowed recognizing specific trapping centers that can be responsible for the observed TSL. In particular, the electron traps of 1.33 and 1.43 eV (in YAlO3) were considered to be formed by the energy level of oxygen vacancy (VO) with different arrangement of neighboring YAl and VY, while shallower electron traps of 0.9-1.0 eV were related to the energy level of YAl antisite complexes with neighboring VO or (VO + VY). The effect of the lowering of electron trap depths in RAlO3 was demonstrated for the VO-related level of the (YAl + VO + VY) complex defect for the particular case of La substituting Y.

Scintillators based on Ce-doped garnets are regularly co-doped with Mg2+ or Ca2+ to form Ce ions in 4+ state and reduce undesired afterglow. However overly high Ce4+ concentration leads to poor light yield performance. In order to understand the reason for variation in luminescence efficiency of Ce3+- and Ce4+-doped garnets we investigate the differences in energy conversion processes in complex LuGd2Ga3Al2O12:Ce3+/Ce4+ ceramics by means of VUV synchrotron irradiation. At first we have established via transmission spectroscopy and X-ray absorption spectroscopy that LuGd2Ga3Al2O12:Ce, Mg sample contains cerium in the 4+ state only. Then we show with VUV spectroscopy efficient interaction of excitons with Gd3+ and Ce3+, and lack of exciton absorption edge in LuGd2Ga3Al2O12:Ce4+ excitation spectrum. Instead, Ce4+ exhibits charge-transfer absorption band in the range of exciton emission. We suggest that when Ce4+ concentration becomes too high, the exciton → Gd3+ → Ce3+ energy transfer path is hindered. It leads to high intensity of Gd3+ luminescence in Lu1Gd2Ga3Al2O12:Ce, Mg ceramics, but lowered Ce3+ X-ray excited luminescence. Fine balance between 3+ and 4+ Ce concentrations is necessary to achieve the best performance of garnet scintillators.

Abstract Though carbonates are known for several decades, their role in sun-light driven photocatalysis is still hidden. Herein, carbonate boosted solar water splitting in nickel-based plasmonic hybrid nanostructures is disclosed for the first time via in-situ experiments and density-functional theory (DFT)-based calculations. Ni@NiO/NiCO₃ core@shell (shell consisting of crystalline NiO and amorphous NiCO₃) nanostructure with varying size and compositions are studied for hydrogen production. The visible light absorption at ∼470 nm excludes the possibility of NiO as an active photocatalyst, emphasizing plasmon driven H₂ evolution. Under white light irradiation, higher hydrogen yield of ∼80 µmol/g/h for vacuum annealed sample over pristine (∼50 µmol/g/h) complements the spectroscopic data and DFT results, uncovering amorphous NiCO₃ as an active site for H₂ absorption due to its unique electronic structure. This conclusion also supports the time-resolved photoluminescence results, indicating that the plasmonic electrons originating from Ni are transferred to NiCO₃ via NiO. The H₂ evolution rate can further be enhanced and tuned by the incorporation of NiO between Ni and NiCO₃.