F. M. Pontes

Crystal growth in colloidal tin oxide nanocrystals induced by coalescence at room temperature

The crystal growth process in colloidal nanocrystal systems is usually associated with the Ostwald-ripening mechanism. Here, we report on experimental evidence indicating that another crystal growth process took place in a colloidal nanocrystal system at room temperature. This crystal growth process is based on grain rotation among neighboring grains, resulting in a coherent grain–grain interface, which, by eliminating common boundaries, causes neighboring grains to coalesce, thereby forming a single larger nanocrystal. This phenomenon was observed in SnO2 nanocrystals (particle size ranging from 10 to 30 A).

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.

Effects of the postannealing atmosphere on the dielectric properties of (Ba, Sr)TiO3 capacitors: Evidence of an interfacial space charge layer

The dielectric properties of ~Ba, Sr!TiO 3 films were found to be remarkably sensitive to the postannealing treatment atmosphere. This study demonstrates that postannealing in an oxygen atmosphere increases the dielectric relaxation phenomenon and that postannealing in a nitrogen atmosphere produces a slight dielectric relaxation. Such dependence of the dielectric relaxation was related both to oxygen vacancies and to the presence of negatively charged oxygen, trapped at the grain boundary and/or at the electrode/dielectric film interface.

Study of the dielectric and ferroelectric properties of chemically processed BaxSr1−xTiO3 thin films

Abstract Polycrystalline Ba x Sr 1− x TiO 3 ( x =0.4 and 0.8) thin films with a perovskite structure were prepared by the polymeric precursor method on a platinum-coated silicon substrate. High-quality thin films with uniform composition and thickness were successfully produced by dip-coating and spin-coating techniques. The resulting thin films prepared by dip and spin-coating showed a well-developed dense polycrystalline structure with uniform grain size distribution. The metal–BST-metal structure of the thin films displays good dielectric and ferroelectric properties. The ferroelectric nature to Ba x Sr 1− x TiO 3 ( x =0.8) thin film, indicated by butterfly-shaped C – V curves and confirmed by the hysteresis curve, showed 2 P r =5.0 μC/cm 2 and E c =20 kV/cm. The capacitance–frequency curve reveals that the dielectric constant may reach a value of up to 794 at 1 kHz. On the other hand, the Ba x Sr 1− x TiO 3 ( x =0.4) thin films had paraelectric nature and dielectric constant and the dissipation factor at a frequency of 100 kHz were 680 and 0.01, respectively, for film annealed at 700°C. In addition, an examination of the films I–V curve at room temperature revealed the presence of two conduction regions in the Ba x Sr 1− x TiO 3 ( x =0.4 and 0.8) thin films, showing ohmic-like behavior at low voltage and a Schottky-emission or Poole–Frenkel mechanism at high voltage.

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.

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.