RESUMO
Inorganic hybrid materials have promising applications in absorbers and for the photon harvesting of solar irradiation, such as in DSSC photoanodes. Moreover, investigation of the interactions between the photoanode constituent materials is extremely important, since it is known that the properties of the materials are strongly dependent on the nucleation and growth process. Therefore, the purpose of this work was to synthesize a system consisting of a synergic combination of two inorganic hosts, BaTiO3 and CaF2, synthesized together through a microwave-assisted hydrothermal method, which allows single-phase materials to be obtained after short synthesis times and at low temperatures. The increase in optical activity was investigated after the insertion of Eu ions. From the structural results, it was possible to observe that the method used to obtain the system was efficient, even using temperatures as low as 140 °C and a reaction time of one minute. The optical properties (emission and excitation) were evaluated in the visible and VUV region from 2.5 to 10.5 eV. The XANES Eu Liii edge differences associated with the XEOL results indicate that the synthesis method incorporated Eu3+ in the hosts and the surface of the two compounds, BaTiO3 and CaF2. Therefore, the combination between the Eu3+ activators and the F centers of the host increased the range for photon harvesting, making these systems a promising material for future applications in photoanodes for DSSCs.
RESUMO
A microwave-assisted hydrothermal method was applied to synthesize BaZr1-xHfxO3, (BZHO) solid solutions at a low temperature, 140 °C, and relatively short times, 160 min. The detailed features of the crystal structure, at both short and long ranges, as well as the crystal chemistry doping process, are extensively analysed. X-ray diffraction measurements and Raman spectroscopy have been used to confirm that pure and Hf-doped BZO materials present a cubic structure. Extended X-ray absorption fine structure (EXAFS) spectra indicate that Hf(4+) ions have replaced the Zr(4+) ions on the 6-fold coordination and a subsequent change on the Ba(2+) 12-fold coordination can be sensed. X-ray absorption near-edge structure (XANES) spectroscopy measurements reveal a local symmetry breaking process, associated to overlap of the 4d-2p and 5d-2p orbitals of Zr-O and Hf-O bonds, respectively. Field emission scanning electron microscopy (FE-SEM) and high resolution transmission electron microscopy (HRTEM) show the mesocrystalline nature of self-assembled BZHO nanoparticles under a dodecahedron shape. In addition first principle calculations were performed to complement the experimental data. The analysis of the band structures and density of states of the undoped BZO and doped BZHO host lattice allow deep insight into the main electronic features. The theoretical results help us to find a correlation between simulated and experimental Raman modes and allow a more substantial interpretation of crystal structure.