Structural and ferroelectric properties of Pb1-xSrxTiO3 thin films

Strontium-modified lead titanate (PST) thin films with composition Pb1-xSrxTiO3 (0.10 < x &LE; 0.60) were grown on Pt/Ti/SiO2/Si substrates using a soft chemical process. The crystallization of the PST thin films was achieved by heat treatment at 600&DEG;C. The structural and microstructural modifications in the films were studied using X-ray diffraction (XRD) and atomic force microscopy, respectively. The XRD study shows that the lattice parameters of polycrystalline PST thin films calculated from X-ray data indicate a decrease in lattice tetragonality with the increase in strontium content in these films. This indicates a gradual change from tetragonal to cubic structure. By atomic force microscopy analysis, the average grain size of the thin films was systematically reduced with the increase in Sr content. The dielectric property of the thin films was found to be strongly dependent on the Sr concentration. With 60 at.% Sr content, a ferroelectric to paraelectric phase transition was observed at room temperature.

Crytallization and high-resolution X-ray diffraction data collection of an Asp49 PLA(2) from Bothrops jararacussu venom both in the presence and absence of Ca2+ ions

Snake venom PLA(2)s have been extensively studied due to their role in mediating and disrupting physiological processes such as coagulation, platelet aggregation and myotoxicity. The Ca2+ ion bound to the putative calcium-binding loop is essential for hydrolytic activity. We report the crystallization in the presence and absence of Ca2+ and X-ray diffraction data collection at 1.60 Angstrom (with Ca2+) and 1.36 Angstrom (without Ca2+) of an Asp49 PLA(2) from Bothrops jararacussu venom. The crystals belong to orthorhombic space group C222(1). Initial refinement and electron density analysis indicate significant conformational. changes upon Ca2+ binding. (C) 2004 Elsevier B.V. All fights reserved.

The evolution of arsenic excess induced by thermal annealing in arsenic-rich Ga1-xAsx films

The evolution of As excess in As-rich Ga1-xAsx films is analyzed for distinct As concentrations and different annealing temperatures. Initially the samples are amorphous and crystallize partially after thermal annealing. The formation of both amorphous and crystalline As clusters is examined by micro-Raman and X-ray diffraction analysis. When highly and moderately unbalanced materials are compared, differences are clearly observed concerning the crystallization temperature and the migration kinetics of the As excess. These differences are explained by the fort-nation of As precipitates around the GaAs crystallites in the moderately unbalanced material, contrasting with the migration of the As excess to the film surface in the highly unbalanced material.

High sinterability of Ca-PZT, synthesized by polymeric and partial oxalate process

This study includes Ca-PZT in the morphotropic phase boundary, MPB process combining the Pechini method, (ZT) and the Partial oxalate method (Ca-PZT) by obtaining single phase particles of ZT phase with a high specific surface area (similar to 110 m(2)/g at 550 degrees C) and narrow particle size distribution. Lead and calcium oxalates were precipitated onto the ZT particle surface and reacted to a solid state interface ZT/Ca-PZT/PbO-CaO. A deviation of a coexistence region from F-T- and F-R-phases to F-R-phase (Zr rich region) was observed. Strong surface area reduction occurs by Ca-PZT crystallization at about 700 degreesC, and demonstrated high sinterability (2.40 m(2)/g - 350 nm) with apparent densities near to 99.9%. Different processing methods did not demonstrate superior results. Studies of calcined powder shows a high sinterability of powder calcined 3 h at 700 degrees C and sintered 3 h at 1000 degreesC coming up to 99.8% of relative density. (C) 2001 Kluwer Academic Publishers.

Antimony oxide based glasses

Glass formation has been investigated in binary systems based on antimony oxide as the main glass former: (100-x)Sb2O3-xWO3, (5 < x < 65), (100 - x)Sb2O3-xSbPO(4), (5 < x < 80) and (100 - x)Sb2O3-x[Sb(PO3)(3)](n), (10 < x < 40). Ternary systems derived from the Sb2O3-WO3 binary glass have also been studied: Sb2O3-WO3-BaF2 Sb2O3-WO3-NaF and Sb2O3-WO3-[Sb(PO3)(3)](n). Glass transition temperature ranges from 280 degreesC to 380 degreesC. It increases as the concentration in tungsten oxide or antimony phosphate increases. Refractive index is larger than 2. Tungsten-containing glasses are yellow in transmission and turn green at the largest WO3 content. Optical transmission and temperatures of glass transition, T-g, onset of the crystallization. T-x, and maximum of crystallization, T-p, have been measured using differential scanning calorimetry (DSC). These glasses have potential photonic applications. (C) 2001 Elsevier B.V. B.V. All rights reserved.

Emplacement setting of the granite sheeted pluton of Esperanca (Brasiliano orogen, Northeastern Brazil)

Anisotropy of magnetic susceptibility (AMS) and isotopic (U-Pb, Sm-Nd) data were combined to study the emplacement setting of the granite sheets that constitute the Esperanca pluton in the Borborema Province (Northeastern Brazil). The sheets dip moderately to the SE along the contact zone between the Paleoproterozoic basement rocks and Early Neoproterozoic orthogneisses and metasediments. Granite fabrics were determined mainly using AMS in 136 sites distributed within the central and western part of the pluton. The sheets normally have susceptibility lower than 0.35 mSI but, locally, where a Ti-poor magnetite appears with titanite, the susceptibility increases up to 5 mSI. Comparison between the silicate fabric and AMS showed inconsistencies between the shape of mineral and magnetic ellipsoids despite of their orientations that fit fairly well to each other. AMS indicated the deformation was partitioned between the lower (tonalite, syenogranite) and upper (leucogranite and coarse porphyritic granite) sheets. In the lower sheets the curvilinear lineation trajectory is attributed to a dominant heterogeneous pure shear event that flattened laterally the still molten tonalite and syenogranite into the regional foliation. ne associated microstructures are typically magmatic. Zircon U/Pb data of the syenogranite yielded a crystallization age of 592 +/- 5 Ma. In the upper sheets the fabric recorded a component of simple shear deformation that displaced the coarse porphyritic granite and the top gneissic host rocks to the southwest. Microstructures are mostly of post-full crystallization type. T(DM) model ages and epsilon(Nd) (t = 0) values indicate that the magma contaminated by partial melting of the regional host rocks. Sheet propagation at the emplacement level would have exploited the contact zone between crustal blocks of different rheologies when the melt pressures would be able to tensionally fail the anisotropy of the host rocks. (C) 2004 Elsevier B.V. All rights reserved.

Dielectric and fatigue properties of Pb(Zr0.53Ti0.47)O-3 thin films prepared from oxide precursors method

Fatigue is an important problem to be considered if a ferroelectric film is used for non-volatile memory devices. In this phenomena, the remanent polarization and coercive field properties degrades in cycles which increase in hysteresis loops. The reasons have been attributed to different mechanisms such as a large voltage applied on ferroelectric film in every reading process in Ferroelectric Random Access Memory (FeRAM) or memories for digital storage in computer, grain size effects and others. The aim of this work is to investigate the influence of the crystallization kinetics on dielectric and ferroelectric properties of the Pb(Zr0.53Ti0.47)O-3 thin films prepared by an alternative chemical method. Films were crystallized in air on Pt/Ti/SiO2/Si substrates at 700 degrees C for 1 hour, in conventional thermal annealing (CTA), and at 700 degrees C for 1 min and 700 degrees C 5 min, using a rapid thermal annealing (RTA) process. Final films were crack free and presented an average of 750 nm in thickness. Dielectric properties were studied in the frequency range of 100 Hz - 1 MHz. All films showed a dielectric dispersion at low frequency. Ferroelectric properties were measured from hysteresis loops at 10 kHz. The obtained remanent polarization (P-r) and coercive field (E-c) were 3.7 mu C/cm(2) and 71.9 kV/cm respectively for film crystallized by CTA while in films crystallized by RTA these parameters were essentially the same. In the fatigue process, the P, value decreased to 14% from the initial value after 1.3 x 10(9) switching cycles, for film by CTA, while for film crystallized by RTA for 5 min, P, decreased to 47% from initial value after 1.7 x 10(9) switching cycles.

Influence of temperature on the dielectric and ferroelectric properties of bismuth titanate thin films obtained by the polymeric precursor method

The (1 1 7) and (0 0 1 0)-oriented Bi4Ti3O12 thin films were fabricated on Pt/Ti/SiO2/Si substrates by using a polymeric precursor solution under appropriate crystallization conditions. Atomic force microscopy and scanning electron microscopy showed relatively large grains, which is typical for this system. The capacitance dependence on voltage is strongly non-linear, confirming the ferroelectric properties of the films resulting from the domain switching. The (1 1 7)-oriented films exhibited a higher remanent polarization (23.7 μ C cm(-2)) than the (0 0 1 0)-oriented films (11.8 μ C cm(-2)). Fatigue tests revealed that the temperature of thermal treatment and degree of orientation affect the performance of the device. © 2005 Elsevier B.V. All rights reserved.

Isotope geochemistry of the mafic dikes from the Vazante nonsulfide zinc deposit, Brazil

The Vazante Group, located in the northwestern part of Minas Gerais, hosts the most important zinc mine in Brazil, the Vazante Mine, which represents a major known example of a hypogene nonsulfide zinc deposit. The main zinc ore is represented by willemite and differs substantially from other deposits of the Vazante-Paracatu region, which are sulfide-dominated zinc-lead ore. The age of the Vazante Group and the hosted mineralization is disputable. Metamorphosed mafic dikes (metabasites) that cut the metasedimentary sequence and are affected by hydrothermal processes recently were found and may shed light on the geochronology of this important geological unit. Zircon crystals recovered from the metabasites are xenocrystic grains that yield U-Pb conventional ages ranging from 2.1 to 2.4 Ga, so the basement of the Vazante Group is Paleoproterozoic or has metasedinientary rocks whose source area was Paleoproterozoic. Pb isotopes determined for titanite separated from the metabasites have common, nonradiogenic Ph compositions, which prevents determination of their crystallization age. However, the Pb signatures observed for the titanite crystals are in agreement with those determined for galena from the carbonate-hosted Zn-Pb deposits hosted by the Vazante Group, including galena from minor sulfide ore bodies of the Vazante deposit. These similarities suggest that the metalliferous fluids that affected the metabasites may have been those responsible for galena formation, which could imply a similar lead source for both nonsulfide and sulfide zinc deposits in the Vazante-Paracatu district. This common source could be related to deep-seated, basin-derived, metalliferous fluids associated with a long-lived hydrothermal system related to diagenesis and deformation of the Vazante Group during the Neoproterozoic. (c) 2005 Elsevier Ltd. All rights reserved.

Diffusion-controlled growth of aggregates in layer-by-layer films of poly(o-methoxyaniline)

The adsorption process in layer-by-layer (LBL) films of poly(o-methoxyaniline) alternated with poly(vinyl sulfonic acid) is explained using the Avrami equation. This equation was used due to its mathematical simplicity and adequate description of experimental data in real polymer systems. The Avrami parameters are a convenient means to represent empirical data of crystallization, and if microscopic knowledge is available these parameters can also be associated with adsorption mechanisms. The growth of spherulites in the LBL films was studied as a function of time using atomic force microscopy and the data were used to estimate the number and radii of aggregates, from which the Avrami parameters were determined. We find that the adsorption mechanism may correspond to a tri dimensional, diffusion-controlled growth, with increasing nucleation rate, consistent with results from kinetics of adsorption.

Thin films prepared from tungstate glass matrix

Vitreous samples containing high concentrations of WO3 (above 40% M) have been used as a target to prepare thin films. Such films were deposited using the electron beam evaporation method onto soda-lime glass substrates. These films were characterized by X-ray diffraction (XRD), perfilometry, X-ray energy dispersion spectroscopy (EDS), M-Lines and UV-vis absorption spectroscopy. In this work, experimental parameters were established to obtain stable thin films showing a chemical composition close to the glass precursor composition and with a high concentration of WO3. These amorphous thin films of about 4 mu m in thickness exhibit a deep blue coloration but they can be bleached by thermal treatment near the glass transition temperature. Such bleached films show several guided modes in the visible region and have a high refractive index. Controlled crystallization was realized and thus it was possible to obtain WO3 microcrystals in the amorphous phase. (C) 2007 Elsevier B.V. All rights reserved.

SrSnO3:Nd obtained by the polymeric precursor method

In this work, the synthesis of Nd-doped SrSnO3 by the polymeric precursor method, with calcination between 250 and 700 A degrees C is reported. The powder precursors were characterized by TG/DTA and high temperature X-ray diffraction (HTXRD). After heat treatment, the material was characterized by XRD and infrared spectroscopy. Ester and carbonate amounts were strictly related to Nd-doping. According to XRD patterns, the orthorhombic perovskite was obtained at 700 A degrees C for SrSnO3 and SrSn0.99Nd0.01O3. For Sr0.99Nd0.01SnO3, the kinetics displayed an important hole in the crystallization process, as no peak was observed in HTXRD up to 700 A degrees C, while a XRD patterns showed a crystalline material after calcination at 250 A degrees C.

Structural and spectroscopic study of oxyfluoride glasses and glass-ceramics using europium ion as a structural probe

Transparent oxyfluoride glasses and beta-PbF(2) nanocrystals containing glass-ceramics were prepared with varying Eu(3+) content (0.3, 0.4, 0.5 and 0.6%). The effect of Eu(3+) content on the preparation of glass-ceramics was investigated. From differential scanning calorimetry, the T(x)-T(g)(T(x)-temperature of the onset of crystallization; T(g)-glass transition temperature) parameter for glasses has shown slight variation, and an exothermic peak near T(g) called the ceramization temperature (T(c)) has been observed. Heat treatments were performed at this temperature to obtain transparent glass-ceramics containing beta-PbF(2) nanocrystals, identified by x-ray diffraction. Heat treatments for different periods of time were performed and were observed to be very important in the control of the crystal size and of the crystallization rate. Based upon the absorption spectra, the scattering level due to the presence of beta-PbF(2) nanocrystals in the glass-ceramics was observed to be similar to that for the mother glasses. Detailed analysis of emission spectra and decay time measurements led to the identification of Eu(3+) ions as the beta-PbF(2) crystalline phase. Excitation spectra at 70 K show the interaction of Eu(3+) ions with the fluorogermanate network.

Innovating transparent glass ceramics based on Ga2S3-GeS2-CsCl

In this paper, we describe the preparation of glass ceramics in the Ga2S3 - GeS2 - CsCl system Visible and infrared transmitting glass ceramics were reproducibly obtained by appropriated heat treatment of the base glass Crystals with controllable size of about 40 nm were homogeneously generated in the glassy matrix X-ray diffraction characterizations have shown that gallium acts as nucleating agent in this material, giving rise to alpha-Ga2S3 crystals Improved thermo-mechanical properties such as dilatation coefficient and resistance to fracture propagation have been observed in the prepared glass ceramics

Structural evolution of Eu-doped hydroxyapatite nanorods monitored by photoluminescence emission

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)