Temperature-dependent Raman spectra of K0.2Na0.8NbO3 ceramics

We performed temperature-dependent Raman scattering studies on K0.2Na0.8NbO3 ceramics and compared the results with those for NaNbO3. The wavenumbers associated with NbO6 vibrations suggest the existence of two phase transitions, as occurs with pure NaNbO3 ceramics. Although the disorder on the Na/K site does not change either the room temperature phase of K0.2Na0.8NbO3 or the sequence of phase transitions compared with NaNbO3, it changes the temperature of the lowest phase transition and strongly modifies the temperature of the antiferroelectric --> new phase II phase transition. Additionally, the linewidth analysis shows that the orientational mechanism is the dominant contribution to linewidth, although the anharmonic contribution is increased, when compared with NaNbO3, owing to the random distribution of potassium in the sodium niobate matrix. Copyright (C) 2004 John Wiley Sons, Ltd.

Photoluminescence in disordered Zn2TiO4

In this work, the polymeric precursor method Was used to obtain disordered Zn2TiO4 powders, either Undoped or doped with Sn4+, Cr3+ and V5+, to be applied its photoluininescent material. The characterization was undertaken by means of thermal analysis (TG and DTA), X-ray diffraction (XRD), infrared spectroscopy (IR) and photoluminescence (PL). Previous works stated that titanate octahedra containing a short Ti-O distance show efficient luminescence at roorn temperature if these octahedra are isolated from each other. In the present work, the phenomenon was observed in condensed octahedra, sharing edges. The room temperature PL noticed in undoped Zn2TiO4 had its intensity increased by the dopant addition-the increase was of about 300% for V5+ doping 400% for Cr3+ and 800% for Sn4+. (c) 2005 Elsevier B.V. All rights reserved.

Photoluminescent behavior of SrBi2Nb2O9 powders explained by means of beta-Bi2O3 phase

Photoluminescence (PL) behavior of SrBi2Nb2O9 (SBN) powders was explained by means of beta-Bi2O3 phase on the SBN lattice. Oxygen vacancies and recombination of electrons holes in the valence band lead to the formation of [NbO5 center dot V-O(x)], [NbO5 center dot V-O(center dot)] and [NbO5 center dot V-O(center dot center dot)] complex clusters which are the main reason for the PL at room temperature. X-ray diffraction and Fourier transform Raman spectroscopy were used as tools to investigate the structural changes in SBN lattice allowing to correlate [NbO5 center dot V-O(center dot)]/[NbO6](') ratio with the evolution of the visible PL emission in the SBN powders. (c) 2007 American Institute of Physics.

Crystal structures and luminescence properties of La3Zr4F25 and alpha-LaZr3F15

During a study of the LaF3-ZrF4 system, both La3Zr4F25 and alpha-LaZr3F15 compounds have been evidenced. Their crystal structures have been determined from single-crystal X-ray diffraction data. La3Zr4F25 crystallises in the cubic system with a= 12.384 Angstrom and I (4) over bar 3d space group (no. 220). Its crystal structure is built up of (ZrF6)(2-) octahedra and (LaF8)(5-) dodecahedra sharing corners. The low temperature form, alpha, of LaZr3F15 is orthorhombic (space group Pmmn, no. 59) with a = 15.721 Angstrom, b = 16.299 Angstrom, c= 8.438 Angstrom. Its structure is built of corner-sharing tricaped trigonal prisms surrounding the La3+ ions and both octahedra and monocapped trigonal prisms encompassing the Zr4+ ions. This structure is characterised by dynamically disordered (ZrF6)(2-) complex anions.The Eu3+ luminescence properties of these phases have been investigated and are discussed in relationship with their crystal structures.

Relaxation and tunnelling of structural units within the LTO phase of La2CuO4

The anelastic relaxation (elastic energy loss and Young modulus) of nearly stoichiometric La2CuO4+delta with LTO structure was measured. Extraordinarily intense effects are present below room temperature in the elastic dynamic susceptibility, indicating relaxational dynamics of a relevant fraction of the lattice. The involved degrees of freedom are identified as rotations of the CuO6 octahedra. Two distinct processes are found at frequencies around 1 kKz: one is observed around 150 K and is characterized by a mean activation energy of 2800 K; the second one occurs below 30 K and is governed by atomic tunnelling. Two explanations are proposed for the faster process: i) formation of fluctuating LTT domains on a scale of few atomic cells; ii) the LTO phase is a dynamical Jahn-Teller phase with all the octahedra tunneling between two LTT-like tilts. In both cases there would be important implications regarding the mechanisms giving rise to charge nanophase separation and strong electron-phonon coupling.

Raman scattering, differential scanning calorimetry and Nd3+ spectroscopy in alkali niobium tellurite glasses

Alkali niobium tellurite glasses have been prepared and some of their properties measured by differential scanning calorimetry and Raman scattering. The vitreous domain was established in the pseudo ternary phases diagram for the system TeO2-Nb2O5-(0.5K(2)O-0.5Li(2)O). Raman scattering shows that for samples in the TeO2 rich part of the phase diagram the vitreous structure is composed essentially of (TeO4) units connected by the vertices, as in the alpha-TeO2 crystal. The addition of alkali and niobium oxides causes depolymerization to occur with structures composed essentially of (TeO3) and (NbO6) units. Samples with the composition (mol%) 80TeO(2)-10Nb(2)O(5)-5K(2)O-5Li(2)O, stable against crystallization, were prepared containing up to 10% mol Nd3+. The addition of this oxide increases the rigidity of the vitreous network shifting characteristic temperatures to higher temperatures. For the 10% Nd3+ sample amorphous phase separation is assumed to exist from the observation of two glass transition temperatures. Spectroscopic properties such as Judd-Ofelt Omega(lambda) intensity parameters, radiative emission probabilities, and induced emission cross sections were calculated. From these results and also from the emission quenching observed as a function of Nd3+ concentration, we suggest that these glasses could be utilized in optical amplifying devices. (C) 1999 Elsevier B.V. B.V. All rights reserved.

Role of oxygen vacancies in the magnetic and dielectric properties of the high-dielectric-constant system CaCu3Ti4O12: An electron-spin resonance study

We report experiments of electron spin resonance (ESR) of Cu2+ in polycrystalline samples of CaCu3Ti4O12 post-annealed in different atmospheres. After being synthesized by solid state reaction, pellets of CaCu3Ti4O12 were annealed for 24 h at 1000 degrees C under air, Ar or O-2. Our temperature dependent ESR data revealed for all samples nearly temperature independent g value (2.15(1)) and linewidth for T > T-N approximate to 25 K. However, the values of ESR linewidth are strongly affected by the oxygen content in the sample. For instance, argon post-annealed samples show a much larger linewidth than the O-2 or air post-annealed samples. We attribute this broadening to an increase of the dipolar homogeneous broadening of the Cu2+ ESR lines due to the presence of oxygen vacancies which induce an S=1/2 spin inside the TiO6 octahedra. Correlation between a systematic dependence of the ESR linewidth on the oxygen content and the high dielectric constant of these materials is addressed. Also, ESR, magnetic susceptibility, and specific heat data for a single crystal of CaCu3Ti4O12 and for polycrystals of CdCu3Ti4O12 are reported.

Structural study of tungstate fluorophosphate glasses by Raman and X-ray absorption spectroscopy

Transparent glasses were synthesized in the NaPO3-BaF2 WO3 tertiary system and several structural characterizations were performed by X-ray absorption spectroscopy (XANES) at the tungsten L-I and L-III absorption edges and by Raman spectroscopy. Special attention was paid to the coordination state of tungsten atoms in the vitreous network.XANES investigations showed that tungsten atoms are only six-fold coordinated (octahedra WO6) and that these glasses are free of tungstate tetrahedra (WO4).In addition, Raman spectroscopy allowed to identify a break in the linear phosphate chains as the amount of WO3 increases and the formation of P-O-W bonds in the vitreous network indicating the modifier behavior of WO6 octahedra in the glass network. Based on XANES data, we suggested a new attribution of several Raman absorption bands which allowed to identify the presence of W-O- and W=O terminal bonds and a progressive apparition of W-O-W bridging bonds for the most WO3 concentrated samples (≥ 30% molar) due to the formation of WO6 clusters. © 2004 Elsevier B.V. All rights reserved.

Structural and morphological characterization of Pb1-xBaxTiO3 thin films prepared by chemical route: An investigation of phase transition

Detailed room temperature micro-Raman scattering, X-ray diffraction, atomic force microscopy and specular reflectance infrared Fourier transform spectroscopy studies were carried out on soft chemical by processed Pb1-xBaxTiO3 thin films. The micro-Raman spectra pointed the existence of a stable tetragonal ferroelectric phase in the entire composition range (0 < x <= 1). The infrared reflectance spectra showed that the frequency of several peaks decreases as the Ba2+ concentration increases. These features are correlated to a decrease in the tetragonal distortion of the TiO6 octahedra as the Ba2+ concentration increases. Furthermore, as x increases from 0.70 to 1.0, the Raman spectrum shows an evolution towards the well-known Raman spectrum of the tetragonal BaTiO3. Therefore, we demonstrated that the combination of solid solution PbTiO3-BaTiO3 with a grain size in the order of 30-40 nm supports the tetragonal ferroelectric phase at room temperature. (C) 2007 Elsevier B.V. All rights reserved.

Structure, microstructure, ferroelectric/electromechanical properties and retention characteristics of [Bi1-x Nb (x) ]FeO3 thin films

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

Photoluminescence in quasi-amorphous Pb0.8X0.2Zr0.53Ti0.47O3 (X = Ca, Sr and Ba) powders: An optical and structural study

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

Crystal structures and luminescence properties of La3Zr4F25 and α-LaZr3F15

During a study of the LaF3-ZrF4 system, both La3Zr4F25 and α-LaZr3F15 compounds have been evidenced. Their crystal structures have been determined from single-crystal X-ray diffraction data. La3Zr4F25 crystallises in the cubic system with a = 12.384 Å and 143d space group (no. 220). Its crystal structure is built up of (ZrF6)2- octahedra and (LaF8)5- dodecahedra sharing corners. The low temperature form, α, of LaZr3F15 is orthorhombic (space group Pmmn, no. 59) with a = 15.721 Å, b = 16.299 Å, c = 8.438 Å. Its structure is built of corner-sharing tricaped trigonal prisms surrounding the La3+ ions and both octahedra and monocapped trigonal prisms encompassing the Zr4+ ions. This structure is characterised by dynamically disordered (ZrF6)2- complex anions. The Eu3+ luminescence properties of these phases have been investigated and are discussed in relationship with their crystal structures.

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.

Cation distribution and magnetic characterization of the multiferroic cobalt manganese Co2MnO4 spinel doped with bismuth

The structural and magnetic properties of the cubic spinel oxide Co 2MnO4 (Fd3m space group) doped with different concentrations of bismuth, were investigated by X-ray diffraction and SQUID magnetometry. The Bi3+ ions entering into the CoIII octahedral sites do not alter the effective moment, μeff ∼8.2 μB, whereas both the magnetization M50 kOe at the highest field (50 kOe) and the field-cooled MFC magnetizations increased when increasing the Bi content. The ferrimagnetic character of the parent compound, Co2MnO4, is maintained for all materials although the antiferromagnetic interactions Co2+-Co2+ are affected, resulting in higher values of the Curie-Weiss temperature. Due to the large ionic radius of Bi, octahedra distortions occur as well as valence fluctuations of the Mn ions, giving rise to Jahn-Teller effects and enhancing the exchange interactions. The off-center Bi3+ ion is responsible of non-centrosymmetric charge ordering and should lead to multiferroïsme conditions for the BixCo2-xMnO4 material. © 2012 Elsevier B.V.

Influence of the network modifier on the characteristics of MSnO 3 (M=Sr and Ca) thin films synthesized by chemical solution deposition

CaSnO3 and SrSnO3 alkaline earth stannate thin films were prepared by chemical solution deposition using the polymeric precursor method on various single crystal substrates (R- and C-sapphire and 100-SrTiO3) at different temperatures. The films were characterized by X-ray diffraction (θ-2θ, ω- and φ-scans), field emission scanning electron microscopy, atomic force microscopy, micro-Raman spectroscopy and photoluminescence. Epitaxial SrSnO3 and CaSnO 3 thin films were obtained on SrTiO3 with a high crystalline quality. The long-range symmetry promoted a short-range disorder which led to photoluminescence in the epitaxial films. In contrast, the films deposited on sapphire exhibited a random polycrystalline growth with no meaningful emission regardless of the substrate orientation. The network modifier (Ca or Sr) and the substrate (sapphire or SrTiO3) influenced the crystallization process and/or the microstructure. Higher is the tilts of the SnO6 octahedra, as in CaSnO3, higher is the crystallization temperature, which changed also the nucleation/grain growth process. © 2012 Elsevier Inc. All rights reserved.