Experimental and theoretical investigations of electronic structure and photoluminescence properties of ß-Ag2MoO4 microcrystals.

In this paper, we investigate a correlation between theoretical calculations and experimental data to explain the electronic structure and optical properties of silver molybdate (ß-Ag2MoO4) microcrystals synthesized by the microwave-assisted hydrothermal method. X-ray diffraction, Rietveld refinement, and micro-Raman spectroscopy confirmed that these microcrystals crystallize in a spinel-type cubic structure. Field-emission scanning electron microscopy images revealed that the processing temperatures influence in the final shape of microcrystals. Optical properties were analyzed by ultraviolet-visible diffuse reflectance spectroscopy; the increase in the optical band gap energy (Egap) (from 3.24 to 3.31 eV) with processing temperature is associated with the reduction of intermediary energy levels. First-principles quantum mechanical calculations based on the density functional theory at the B3LYP level were conducted. The calculated band structure revealed an indirect Egap of approximately 4.00 and 3.34 eV for the ß-Ag2MoO4 without and with the formation of defects, respectively. Theoretical calculations based on density of states and electron density maps were employed to understand the polarization phenomenon induced by structural defects in the ß-Ag2MoO4 crystals. Finally, photoluminescence properties at room temperature of ß-Ag2MoO4 microcrystals were explained by the charge-transfer mechanism involving tetrahedral [MoO4] clusters.

Structural evolution, growth mechanism and photoluminescence properties of CuWO4 nanocrystals.

Copper tungstate (CuWO4) crystals were synthesized by the sonochemistry (SC) method, and then, heat treated in a conventional furnace at different temperatures for 1h. The structural evolution, growth mechanism and photoluminescence (PL) properties of these crystals were thoroughly investigated. X-ray diffraction patterns, micro-Raman spectra and Fourier transformed infrared spectra indicated that crystals heat treated and 100°C and 200°C have water molecules in their lattice (copper tungstate dihydrate (CuWO4·2H2O) with monoclinic structure), when the crystals are calcinated at 300°C have the presence of two phase (CuWO4·2H2O and CuWO4), while the others heat treated at 400°C and 500°C have a single CuWO4 triclinic structure. Field emission scanning electron microscopy revealed a change in the morphological features of these crystals with the increase of the heat treatment temperature. Transmission electron microscopy (TEM), high resolution-TEM images and selected area electron diffraction were employed to examine the shape, size and structure of these crystals. Ultraviolet-Visible spectra evidenced a decrease of band gap values with the increase of the temperature, which were correlated with the reduction of intermediary energy levels within the band gap. The intense photoluminescence (PL) emission was detected for the sample heat treat at 300°C for 1h, which have a mixture of CuWO4·2H2O and CuWO4 phases. Therefore, there is a synergic effect between the intermediary energy levels arising from these two phases during the electronic transitions responsible for PL emissions.

Morphology and Photoluminescence of HfO(2) Obtained by Microwave-Hydrothermal.

In this letter, we report on the obtention of hafnium oxide (HfO(2)) nanostructures by the microwave-hydrothermal method. These nanostructures were analyzed by X-ray diffraction (XRD), field-emission gum scanning electron microscopy (FEG-SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectrometry (EDXS), ultraviolet-visible (UV-vis) spectroscopy, and photoluminescence (PL) measurements. XRD patterns confirmed that this material crystallizes in a monoclinic structure. FEG-SEM and TEM micrographs indicated that the rice-like morphologies were formed due to an increase in the effective collisions between the nanoparticles during the MH processing. The EDXS spectrum was used to verify the chemical compositional of this oxide. UV-vis spectrum revealed that this material have an indirect optical band gap. When excited with 488 nm wavelength at room temperature, the HfO(2) nanostructures exhibited only one broad PL band with a maximum at around 548 nm (green emission).

Synthesis, growth process and photoluminescence properties of SrWO4 powders.

SrWO(4) powders were synthesized by the co-precipitation method and processed in a microwave-hydrothermal (MH) at 140 degrees C for different times. The obtained powders were analyzed by X-ray diffraction (XRD), micro-Raman (MR) spectroscopy, Fourier transform infrared (FT-IR) spectroscopy, field-emission gun scanning electron microscopy (FEG-SEM), ultraviolet-visible (UV-vis) absorption spectroscopy and photoluminescence (PL) measurements. XRD patterns and MR spectra showed that the SrWO(4) powders present a scheelite-type tetragonal structure without the presence of deleterious phases. FT-IR spectra exhibited a high absorption band situated at 831.57 cm(-1), which was ascribed to the WO antisymmetric stretching vibrations into the [WO(4)] tetrahedron groups. FEG-SEM micrographs suggested that the processing time is able to influence in the growth process and morphology of SrWO(4) powders. UV-vis absorption spectra revealed different optical band gap values for these powders. A green PL emission at room temperature was verified in SrWO(4) powders when excited with 488 nm wavelength.

Synthesis of (Ca,Nd)TiO3 powders by complex polymerization, Rietveld refinement and optical properties.

Neodymium calcium titanate, (Ca(0.99)Nd(0.01))TiO(3) powders were synthesized by the complex polymerization method and heat treated at different temperatures for 2 h under air atmosphere. The structural evolution of these powders as a function of heat treatment temperature was analyzed by X-ray diffraction (XRD) and micro-Raman (MR) spectroscopy. The optical properties were investigated by Ultraviolet-visible (UV-vis) absorption spectroscopy and Photoluminescence (PL) measurements. XRD patterns, Rietveld refinement and MR spectra indicated that the powders heated treated at 750 degrees C for 2 h present an orthorhombic structure without secondary phases. UV-vis measurements suggested the presence of intermediary energy in disordered (Ca(0.99)Nd(0.01))TiO(3) powders. Broad and narrow bands were observed in the PL spectra of these powders when excited with 350 nm wavelength. The broad bands were associated to the structural defects and/or p-d electronic transitions while, the narrow bands were ascribed to f-f transitions arising from Nd(3+) ions.