The origin of photoluminescence in amorphous lead titanate

We discuss the nature of visible photoluminescence at room temperature in amorphous lead titanate in the light of the results of recent experimental and theoretical calculations. Experimental results obtained by XANES and EXAFS revealed that amorphous lead titanate is composed of a Ti-O network having fivefold Ti coordination and NBO-type (non-bridging oxygen) defects. These defects can modify the electronic structure of amorphous compounds. Our calculation of the electronic structure involved the use of first-principle molecular calculations to simulate the variation of the electronic structure in the lead titanate crystalline phase, which is known to have a direct band gap, and we also made an in-depth examination of amorphous lead titanate. The results of our theoretical calculations of amorphous lead titanate indicate that the formation of fivefold coordination in the amorphous system may introduce delocalized electronic levels in the HOMO ( highest occupied molecular orbital) and the LUMO ( lowest unoccupied molecular orbital). A comparison of the experimental and theoretical results of amorphous compounds suggests the possibility of a radiative recombination (electron-hole pairs), which may be responsible for the emission of photoluminescence. (C) 2003 Kluwer Academic Publishers.

Topotatic-like phase transformation of amorphous lead titanate to cubic lead titanate

The crystallization process of lead titanate (PT) prepared using the polymeric precursor method was investigated using X-ray diffractometry, Raman spectroscopy, electron microscopy, and X-ray absorption spectroscopy techniques. The results showed that amorphous PT was formed by an O-Ti-O structure composed of fivefold and sixfold oxygen-coordinated titanium. The local structure of the amorphous PT phase was similar to that of the cubic PT phase, i.e., similar coordination number and similar bond lengths, leading to a topotactic-like transformation during the phase transformation from amorphous to cubic perovskite PT. Because of the low crystallization temperature, every transformation observed during the crystallization process was associated with a short-range rearrangement process.

Direct amorphous-to-cubic perovskite phase transformation for lead titanate

The phase evolution of lead titanate processed by the polymeric precursor method was investigated by thermal analysis, X-ray diffraction, and high-resolution transmission electron microscopy. The results showed that the cubic perovskite PbTiO3 (PT) phase is formed from an inorganic amorphous precursor at a temperature of 444 °C. A gradual transition from cubic to tetragonal perovskite PT was observed with the increase of calcination time at this temperature. HRTEM results showed that the cubic PT particles have a size of around 5 nm. The identification of cubic PT as an intermediate phase supports the hypothesis that the chemical homogeneity was kept at the molecular level during the synthesis process, with no cation segregation.

Gibbs energy formation of lead titanate

The Gibbs energy of formation of titania-saturated lead titanate has been determined by e.m.f. measurements on the solid state cell;Pt,Ir,Pb + Pb1−xTiO3−x + TiO2(rutile)/CaO-ZrO2/Ni + NiO,Pt in the temperature range 1075–1350 K. The results obtained are significantly different from those reported in the literature based upon vapour pressure measurements, employing Knudsen effusion and transportation techniques, and assuming that the vapor phase consisted entirely of monomeric PbO molecules. A reanalysis of the data obtained in the earlier vapor pressure studies using mass spectrometric measurements on polymeric PbO species in the gas phase, gives Gibbs energies of formation of lead titanate which are in better agreement with those obtained in this study. Earlier electrochemical measurements by Mehrotra et al. and more recent electrochemical measurements by Schmahl et al. both employing CaO-ZrO2 solid electrolytes are in good agreement with the present study. The electro-chemical measurements by Schmahl et al. using PbF 2 solid electrolyte give a slightly more positive Gibbs energy of formation. There was no evidence supporting the formation of compounds other than Pb1−xTiO3−x from yellow PbO and rutile form of TiO2 in the temperature range covered in this study.Résumé L'enthalpie libre de formation du titanate de plomb saturé en oxyde de titane a été déterminée par des mesures de FEM de la pile: Pt,Ir,Pb + Pb1−xTiO3−x + TiO2(rutile)/CaO-ZrO2/Ni + NiO,Pt dans le domaine de températures 1075–1350 K. Les résultats obtenus, different appréciablement de ceux publiés, déterminés par mesures de tensions de vapeur (techniques de transport et d'effusion de Knudsen) en supposant que la phase gazeuse etait uniquement constituée de molécules monomériques de PbO. Une réanalyse des résultats de la littérature, à partir de mesures par spectrométrie de masse sur les polymères de PbO gazeux, donne des enthalpies libres de formation du titanate de plomb se rapprochant de celles obtenues dans cette étude. Les mesures de Mehrotra et al. et plus récemment de Schmahl et al. utilisant toutes deux l'électrolyte CaO-ZrO2 concordent bien avec celles de la présente étude. Les mesures de Schmahl et al., à l'aide de l' électrolyte solide PbF2, donnent une enthalpie de formation légèrement plus positive. Pour la gammede températures étudiée, rien ne permet de supposer que des composés autres que Pb1−x TiO3−x puissent se former à partir du PbO Gaune) et du rutile (TiO2).

Schottky barrier heights of tantalum oxide, barium strontium titanate, lead titanate, and strontium bismuth tantalate

The Schottky barrier heights of various metals on the high permitivity oxides tantalum pentoxide, barium strontium titanate, lead zirconate titanate, and strontium bismuth tantalate have been calculated as a function of the metal work function. It is found that these oxides have a dimensionless Schottky barrier pinning factor S of 0.28-0.4 and not close to 1 because S is controlled by Ti-O-type bonds not Sr-O-type bonds, as assumed in earlier work. The band offsets on silicon are asymmetric with a much smaller offset at the conduction band, so that Ta2O5 and barium strontium titanate are relatively poor barriers to electrons on Si. © 1999 American Institute of Physics.

Dielectric response features and oxygen migration on rare earth modified lead titanate ferroelectric ceramics

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Structural and dielectric characterization of praseodymium-modified lead titanate ceramics synthesized by the OPM route

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Attainment of lead titanate - Through the thermal decomposition of coprecipitated 8-hydroxyquinolinate precursors

Crystalline PbTiO3 was obtained through the thermal decomposition of 8-hydroxyquinolinate of lead(II) and that of titanium(IV), which was monitored by TG/DTG/DTA under different atmospheric conditions and with varying heating rates. The compound was prepared from adding 8-hydroxyquinoline solution in the solution of metallic ions Pb(II):Ti(IV) (1:1) Linder constant stirring at 3degreesC, having the pH adjusted to 10. The results of these investigations show that different thermal behavior related to the precursor occurred and also the consequent formation of residues which have different crystallinities. No carbonate residues from the thermal decomposition could be determined by XRD and IR. Only PbTiO3 was observed and confirmed by DSC at 470degreesC, temperature lower than the tetragonal-cubic transition.

Photoluminescence in amorphous zirconium titanate

Photoluminescence at room temperature was observed in amorphous zirconium titanate obtained from the polymeric precursor method. This was the first time in which PL was noticed in an amorphous compound made of two network formers. The PL spectra could be deconvoluted into two bands, whose center 1 was located from 540 nm to 552 nm and center 2 from 625 nm to 641 nm. The co-existence of fivefold and sixfold oxygen coordination of titanium and/or zirconium could be the origin of the radiative recombination of electron-hole pairs in amorphous ZT, which may be responsible for the emission of the photoluminescence.

Microstructural, dielectric and ferroelectric properties of calcium-modified lead titanate thin films derived by chemical processes

Ferroelectric Pb1-xCaxTiO3 (x = 0.24) thin films were formed on a Pt/Ti/SiO2/Si substrate by the polymeric precursor method using the dip-coating technique for their deposition. Characterization of the films bq X-ray diffraction showed a perovskite single phase with a tetragonal structure after annealing at 700 degreesC. Atomic force microscopy (AFM) analyses showed that the film had a smooth and crack-free surface with low surface roughness. In addition, the PCT thin film had a granular structure with an 80 nm grain size. The thickness of the films observed by the scanning electron microscopy (SEM) is 550 nm and there is a good adhesion between the film and substrate. For the electrical measurements metal-ferroelectric-metal of the type capacitors were obtained, where the thin films showed good dielectric and ferroelectric properties. The dielectric constant and dissipation factor at 1 kHz and measured at room temperature were found to be 457 and 0.03. respectively. The remanent polarization and coercive field for the: deposited films were P-r = 17 muC/cm(2) and E-c = 75 kV/cm, respectively. Moreover. The 550-nm-thick film showed a current density in the order of 10(-8) A/cm(2) at the applied voltage of 2 V. The high values of the thin film's dielectric properties are attributed to its excellent microstructural quality and the chemical homogeneity obtained by the polymeric precursor method. (C) 2001 Elsevier science Ltd. All rights reserved.

Structural and electrical characterization of semiconducting barium-lead-titanate ceramics

BaTiO3 is usually doped to achieve the temperature stability required by device applications, as well as to obtain a large positive temperature coefficient anomaly of resistivity (PTCR). Uniform distribution of dopants among the submicron dielectric particles is the key for optimal control of grain size and microstructure to maintain a high reliability. The system Ba0.84Pb0.16TiO3 was synthesized from high purity BaCO3, TiO2, PbO oxide powders as raw materials. Sb2O3, MnSO4 and ZnO were used as dopants and Al2O3, TiO2 and SiO2 as grain growth controllers. Phase composition was analyzed by using XRD and the microstructure was investigated by SEM. EDS attached to SEM was used to analyze phase composition specially related to abnormal grain growth. Electrical resistivities were measured as a function of temperature and the PTCR effect characterized by an abrupt increase on resistivity.

Structural phase evolution of strontium-doped lead titanate thin films prepared by the soft chemical technique

Strontium-modified lead titanate thin films with composition Pb1-xSrxTiO3 were grown on Pt/Ti/SiO2/Si substrates using the polymeric precursor method. The structural phase evolution as a function of the Sr contents was studied using micro-Raman scattering, specular reflectance infrared Fourier transform spectroscopy, and x-ray diffraction. The results showed a gradual change from tetragonal to cubic structure, the transition occurring at about x = 0.58. The infrared reflectance spectra showed that the frequency of several peaks decreases as the strontium concentration increases. These features are correlated with a decrease in the tetragonal distortion of the TiO6 octahedra as the strontium concentration increases.

Calcium modified lead titanate/poly-ether-ether-ketone composite for acoustic emission sensors

Composites made of calcium modified lead titanate ceramic powder and poly (ether-ether-ketone) high performance polymer matrix were prepared in the film form using a hot press. The acoustic and electromechanical properties of the composites have been determined using the ultrasonic immersion technique and piezoelectric spectroscopy, respectively. The composite film with 60 - 40 vol.% PTCa/PEEK was tested as acoustic emission detector. Preliminary results shown that the piezo composite can be used as sensor to evaluate the behavior of materials.

Photoluminescent behavior of SrZrO(3)/SrTiO(3) multilayer thin films

A detailed investigation was made into the origin of photoluminescence in an alternate multilayer system of SrZrO(3) (SZO) and SrTiO(3) (STO) thin films. XRD and room-temperature PL studies revealed a high consistency with respect to improved crystallization at elevated temperatures. The photoluminescence behaviour of SZO/STO multilayered system consists in the superposition of independent photoluminescence emissions of both STO and SZO films. Based on the present results and on previous experimental and theoretical data, we propose that the origin of the photoluminescence emission results from structural disorder generated by the presence of distortions in the ideal constituent clusters of these materials. (c) 2009 Elsevier B.V. All rights reserved.

Nanosized lead lanthanum titanate (PLT) ceramic powders synthesized by the oxidant peroxo method

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