P. S. Pizani

Photoluminescence of disordered ABO3 perovskites

Intense photoluminescence in highly disordered (amorphous) BaTiO3, PbTiO3, and SrTiO3 prepared by the polymeric precursor method was observed at room temperature. The emission band maxima from the three materials are in the visible region and depend on the exciting wavelength. The origin of the photoluminescence was not exactly identified. However, the line shape indicates that confinement effects are not probable. The experimental results indicate that it could be related to the disordered perovskite structure.

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.

Preparation, structural and optical characterization of BaWO4 and PbWO4 thin films prepared by a chemical route

Polycrystalline BaWO4 and PbWO4 thin films having a tetragonal scheelite structure were prepared at different temperatures. Soluble precursors such as barium carbonate, lead acetate trihydrate and tungstic acid, as starting materials, were mixed in aqueous solution. The thin films were deposited on silicon, platinum-coated silicon and quartz substrates by means of the spinning technique. The surface morphology and crystal structure of the thin films were investigated using scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray diffraction, and specular reflectance infrared Fourier transform spectroscopy, respectively. Nucleation stages and surface morphology evolution of thin films on silicon substrates have been studied by atomic force microscopy. XRD characterization of these films showed that BaWO4 and PbWO4 phase crystallize at 500 � C from an inorganic amorphous phase. FTIR spectra revealed the complete decomposition of the organic ligands at 500 � C and the appearance of two sharp and intense bands between 1000 and 600 cm � 1 assigned to vibrations of the antisymmetric stretches resulting from the high crystallinity of both thin films. The optical properties were also studied. It was found that BaWO4 and PbWO4 thin films have Eg=5.78 eV and 4.20 eV, respectively, of a direct transition nature. The excellent microstructural quality and chemical homogeneity results confirmed that soft solution processing provides an inexpensive and environmentally friendly route for the preparation of BaWO4 and PbWO4 thin films. # 2003 Elsevier Ltd. All rights reserved.

The role of network modifiers in the creation of photoluminescence in CaTiO3

We discuss the nature of visible photoluminescence (PL) at room temperature in amorphous calcium titanate in the light of the results of recent experimental and quantum mechanical theoretical studies. Our investigation of the electronic structure involved the use of first-principle molecular calculations to simulate the variation of the electronic structure in the calcium titanate crystalline phase, which is known to have a direct band gap, and we also made an in-depth examination of amorphous calcium titanate. The results of our theoretical calculations of amorphous calcium titanate indicate that the formation of fivefold coordination in the amorphous system may introduce delocalized electronic levels in the highest occupied and the lowest unoccupied molecular orbitals. These delocalized electronic levels are related to the formation of a tail in the absorbance spectrum curve. The results indicate that amorphous calcium titanate has the conduction band near the band gap dominated by Ca states contribution. Experimental optical absorption measurements showed the presence of a tail. These results are interpreted by the nature of these exponential optical edges and tails, associated with defects promoted by the disordered structure of the amorphous material. We associate them with delocalized states in the band gap.

Experimental and theoretical correlation of very intense visible green photoluminescence in BaZrO3 powders

Very intense visible green photoluminescence (PL) was observed at room temperature in structurally ordered-disordered BaZrO3 powders. Ab initio calculations, ultraviolet-visible absorption spectroscopy, electron paramagnetic resonance, and PL were performed. Theoretical and experimental results showed that local defects in the cubic structure caused by [ZrO5⋅VOz] complex clusters, where VOz=VOx, VO•, and VO••, play an important role in the formation of hole-electron pairs, giving rise to a charge gradient in the structure which is responsible for PL emission.

Toward an Understanding of Intermediate- and Short-Range Defects in ZnO Single Crystals. A Combined Experimental and Theoretical Study †

A joint use of experimental and theoretical techniques allows us to understand the key role of intermediate- and short-range defects in the structural and electronic properties of ZnO single crystals obtained by means of both conventional hydrothermal and microwave-hydrothermal synthesis methods. X-ray diffraction, Raman spectra, photoluminescence, scanning electronic and transmission electron microscopies were used to characterize the thermal properties, crystalline and optical features of the obtained nano and microwires ZnO structures. In addition, these properties were further investigated by means of two periodic models, crystalline and disordered ZnO wurtzite structure, and first principles calculations based on density functional theory at the B3LYP level. The theoretical results indicate that the key factor controlling the electronic behavior can be associated with a symmetry breaking process, creating localized electronic levels above the valence band.

Amorphous lead titanate: a new wide-band gap semiconductor with photoluminescence at room temperature

This paper describes a new amorphous wide-band gap semiconductor with photoluminescence (PL) at room temperature. The amorphous PbTiO3 was prepared by a sol–gel-like process in powder and thin film form. The optical property and the PL behaviour showed a direct relation to the amorphous structure. The PL peak energy can be controlled by the change of the exciting surge energy. Copyright

Theoretical and experimental study on the photoluminescence in BaTiO3 amorphous thin films prepared by the chemical route

Abstract A polymeric precursor method was used to synthesize BaTiO 3 amorphous thin film processed at low temperature. The luminescence spectra of BaTiO 3 amorphous thin films at room temperature revealed an intense single-emission band in the visible region. The visible emission band was found to be dependent of the thermal treatment history. Photoluminescence (PL) properties for different annealing temperatures were investigated. It was concluded that the intensity of PL is strongly dependent on both the heat treatment of the films and the presence of an inorganic disordered phase. Experimental optical absorption measurements showed the presence of a tail. These results are interpreted by the nature of these exponential optical edges and tails, associated with defects promoted by the disordered structure of the amorphous material. We discuss the nature of visible PL at room temperature in amorphous barium titanate in the light of the results of recent experimental and quantum mechanical theoretical studies. Our investigation of the electronic structure involved the use of first-principle molecular calculations to simulate the variation of the electronic structure in the barium titanate crystalline phase, which is known to have a direct band gap, and we also made an in-depth examination of amorphous barium titanate.

Influence of Ca concentration on the electric, morphological, and structural properties of (Pb,Ca)TiO3 thin films

Pb1−xCaxTiO3 (0.10⩽x⩽0.40) thin films on Pt/Ti/SiO2/Si(100) substrates were prepared by the soft solution process and their characteristics were investigated as a function of the calcium content (x). The structural modifications in the films were studied using x-ray diffraction and micro-Raman scattering techniques. Lattice parameters calculated from x-ray data indicate a decrease in lattice tetragonality with the increasing content of calcium in these films. Raman spectra exhibited characteristic features of pure PbTiO3 thin films. Variations in the phonon mode wave numbers, especially those of lower wave numbers, of Pb1−xCaxTiO3 thin films as a function of the composition corroborate the decrease in tetragonality caused by the calcium doping. As the Ca content (x) increases from 0.10 to 0.40, the dielectric constant at room temperature abnormally increased at 1 kHz from 148 to 430. Also calcium substitution decreased the remanent polarization and coercive field from 28.0 to 5.3 μC/cm2 and 124 to 58 kV/c...

Ferroelectric and optical properties of Ba0.8Sr0.2TiO3 thin film

Barium strontium titanate (Ba0.8Sr0.2TiO3) thin films have been prepared on Pt/Ti/SiO2/Si substrates using a soft solution processing. X-ray diffraction and also micro-Raman spectroscopy showed that the Ba0.8Sr0.2TiO3 thin films exhibited a tetragonal structure at room temperature. The presence of Raman active modes was clearly shown at the 299 and 725 cm−1 peaks. The tetragonal-to-cubic phase transition in the Ba0.8Sr0.2TiO3 thin films is broadened, and suppressed at about 35 °C, with a maximum dielectric constant of 948 (100 kHz). Electrical measurements for the prepared Ba0.8Sr0.2TiO3 thin films showed a remnant polarization (Pr) of 6.5 μC/cm2, a coercive field (Ec) of 41 kV/cm, and good insulating properties. The dispersion of the refractive index is interpreted in terms of a single electronic oscillator at 6.97 eV. The direct band gap energy (Eg) and the refractive index (n) are estimated to be 3.3 eV and n = 2.27–2.10, respectively.