Effect of buffer layers on the property of Pb(Zr,Ti)O3-Pb(Mn,W,Sb,Nb)O3 thin films grown by pulsed laser deposition

New ferroelectric Pb(Zr,Ti)O₃-Pb(Mn,W,Sb,Nb)O₃ (PZT-PMWSN) thin film has been deposited on a Pt/Ti/SiO₂/Si substrate by pulsed laser deposition. Buffer layer was adopted between film and substrate to improve the ferroelectric properties of PZT-PMWSN films. Effect of a Pb(Zr_0.52Ti_0.48)O₃ (PZT) and (Pb_0.72La_0.28)Ti_0.93O₃ (PLT) buffer layers on the stabilization of perovskite phase and the suppression of pyrochlore phase has been examined. Role of buffer layers was investigated depending on different types of buffer layer and thickness. The PZT-PMWSN thin films with buffer layer have higher remnant polarization and switching polarization values by suppressing pyrochlore phase formation. The remnant polarization, saturation polarization, coercive field and relative dielectric constant of 10-nm-thick PLT buffered PZT-PMWSN thin film with no pyrochlore phase were observed to be about 18.523 μC/cm², 47.538 μC/cm², 63.901 kV/cm and 854, respectively.     

Synthesis,photophysical properties,and photocatalytic applications of Bi doped NaTaO3 and Bi doped Na2Ta2O6 nanoparticles

Phase formation and photophysical properties of bismuth doped sodium tantalum oxide (perovskite, defect pyrochlore) nanoparticles prepared by a hydrothermal method were studied in detail. It was revealed that the synthesis conditions like NaOH concentration and bismuth precursor (NaBiO₃·2H₂O) markedly affect the crystal structure of sodium tantalum oxide. At low NaOH concentration and high bismuth precursor (NaBiO₃·2H₂O) content, Bi doped Na₂Ta₂O₆ (defect pyrochlore) phase was predominantly formed, while at higher NaOH concentration, Bi doped NaTaO₃ (perovskite) phase was formed. It was observed that the defect pyrochlore (Bi doped Na₂Ta₂O₆) phase was formed and stabilized by the presence of dopant precursor (NaBiO₃·2H₂O). The chemical analysis of the samples confirmed the doping of Bi³⁺ cations in both phases. Doping of bismuth enabled visible light absorption up to 500 nm in perovskite and defect pyrochlore type sodium tantalum oxide. Bi doped NaTaO₃ samples showed better performance for the photocatalytic degradation of rhodamine B than that of Bi doped Na₂Ta₂O₆, under visible light irritation (λ>420 nm). The present results shed light on phase formation of sodium tantalate and these results are useful in understanding properties of NaTaO₃ based compounds, synthesized by the hydrothermal method.     

Les pyrochlores ferroelectriques derives de Cd2Nb2O6S: Mise en évidence des transitions de phase par des techniques d'optique non linéaire

The ferroelectric pyrochlore compound Cd₂Nb₂O₆S and solid solution Cd₂Nb₂O_7?xS_x have been studied by second optical harmonic generation. The excitation source was a YAG: Nd³⁺ laser emitting at λ = 1.06 μm. The intensity variation of second harmonic as a function of temperature was investigated. A strong signal appears in the two ferroelectric phases. The transition temperatures are easily observed; dielectric and calorimetric results are confirmed.     

A lattice dynamical investigation of the Raman and the infrared frequencies of the cubic Y2Ru2O7 pyrochlore

A short-range force constant model has been applied for the first time to investigate the Raman and the infrared frequencies in Y₂Ru₂O₇ pyrochlore in its cubic phase of space group Fd3m. The calculations of zone center phonons have been made with four stretching and three bending force constants. The calculated values of Raman and infrared frequencies are in good agreement with the observed ones.     

Redistribution of chromium atoms between the components of an intermetallic/oxide nanocomposite in the course of its production

Structural studies of nanocomposites produced by the method combining mechanical preactivation of the mixture comprising 8.1% Cr₂O₃, 65.9% Fe, and 25% Al by mass and self-propagating high-temperature synthesis (SPHTS) have been carried out by Mössbauer spectroscopy methods. It was found that a Fe/Al/Cr₂O₃ composite with a small Fe₂Al₅ intermetallic impurity is produced at the mechanical activation stage. At the SPHTS stage, interaction between the activated components of the mixture results in formation of the Fe_0.70?x Cr _x Al_0.3/Al₂O₃ (x = 0–0.2) composite.     

Fast ion conduction in the defect pyrochlore system KBxW2−xO6(B = Al,Ti and Ta)

K⁺ ionic conductivity has been measured by the complex impedence method for the defect pyrochlore type compounds of the general formula K(B^y+_xW⁶⁺_2?x)O₆, (x=1/(6?y)) where B=Al³⁺, Ti⁴⁺ and Ta⁵⁺. Thermogravimetric analysis showed the compounds to be hydrated at room temperature with from ∽0.2 mole for the Al compound to ∽1 mole of water for the Ta substituted phase. There is a correlation between the lattice parameter and amount of water present in the cavities. The ionic conductivity of 5.2×10^?3ω^?1cm^-1 at 300°C for KAl_0.33W_1.67O₆ is found to be best among known KB₂O₆ type pyrochlores. High ionic conductivity has been explained on the basis of occupancy of K⁺ ions in the available sites and polarization of the B₂X₆ network.     

Cation disorder in NaW2O6+δ·nH2−zO post-ion exchange with K, Rb, Sr, and Cs

The structure of the defect pyrochlore NaW₂O_6+δ·nH_2−zO after ion exchange with K, Rb, Sr or Cs for Na has been investigated using thermal analysis, solid-state nuclear magnetic resonance, laboratory X-ray and neutron diffraction methods. Neutron diffraction studies show that both the A-type cations (Na⁺, K⁺, Rb⁺, and/or Cs⁺) and the water molecules reside within the channels that form in the 111 direction of the W₂O₆ framework and that these strongly interact. The analytical results suggest that the water and A-type cations compete for space in the tunnels within the W₂O₆ pyrochlore framework, with the total number of water molecules and cations being approximately constant in the six samples investigated. The interplay between the cations and water explains the non-linear dependence of the a lattice parameter on the choice of cation. It appears that the ion-exchange capacity of the material will be controlled by the amount of water initially present in the sample.     

Effect of ZnO on phase emergence, microstructure and surface modifications of calcium phosphosilicate glass/glass-ceramics having iron oxide

The effect of ZnO on phase emergence and microstructure properties of glass and glass-ceramics with composition 25SiO₂-50CaO-15P₂O₅-(10 − x)Fe₂O₃-xZnO (where x = 0, 2, 5, 7 mol%) has been studied. They have been characterized using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM). Surface modifications of these glass-ceramics in simulated body fluid have been studied using Fourier transform infrared reflection spectroscopy (FTIR), XPS and SEM. Results have shown a decrease in the fraction of non-bridging oxygen with increase in zinc oxide content. Emergence of crystalline phases in glass-ceramics at different heat treatment temperatures was studied using XRD. When glass is heat treated at 800 °C calcium phosphate, hematite and magnetite are developed as major phases in the glass-ceramics samples with ZnO up to 5 mol%. In addition to these, calcium silicate (Ca₃Si₂O₇) phase is also observed when glass is heat treated at 1000 °C. The microstructure of the glass-ceramics heat treated at 800 °C exhibits the formation of nano-size (40-50 nm) grains. On heat treatment at 1000 °C crystallites grow to above 50 nm size and more than one phase are observed in the microstructure. The formation of thin flake-like structure with coarse particles is observed at high zinc oxide concentration (x = 7 mol%). In vitro studies have shown the surface modifications and formation of Ca-P-rich layer on the glass-ceramics when immersed in simulated body fluids (SBF) for different durations. The bioactive response was found to depend on ZnO content.     

Dielectric and magnetoelectric properties of BaTiO3–CoMn0.2Fe1.8O4 particulate (0-3) multiferroic composites

Multiferroic properties of (x) CoMn_0.2Fe_1.8O₄–(1-x) BaTiO₃ particulate magnetoelectric (ME) composites with x = 0.1, 0.2, 0.3 M percentage was investigated. The CoMn_0.2Fe_1.8O₄ (CMFO) phase was synthesized by solution combustion route and BaTiO₃ (BT) phase was synthesized by wet chemical method. X-ray diffraction studies revealed the purity of constitute phases; confirmed the manifestation of CMFO and BT within the ME composite structure. The microstructural aspects were observed by using Fe-SEM; revealed the effect of constituent phases on the average grain size of the composites. The temperature dependent dielectric properties for BT exhibited the three anomalies associated to its crystallographic lattice structure change with temperature. Dielectric constant of the composite was found to be decreased with CMFO content. All the composite structures exhibited typical magnetic hysteresis nature at room temperature and showed linear effect on the saturation magnetization of the composite with CMFO content. The ME response was examined at room temperature with an ac magnetic field at 1 kHz, all the composite showed a sharp decreasing behavior of the ME voltage coefficient (α_ME) to an applied dc bias in low field region. The maximum α_ME factor of ～8.51 mV/cm Oe was observed for 10% CMFO–90% BT composition.     

Les phases Cd2Nb2-2xSn2xO7-2xF2x

The solid solution Cd₂Nb_2-2xSn_2xO_7-2xF_2x is studied by X-Ray diffraction and Mössbauer spectroscopy. Two phases I and II are observed; phase I presents a normal pyrochlore structure but phase II shows a local order around Sn⁴⁺. The difference between phases I and II is explained by the difference of electronic configuration between Sn⁴⁺ (4d¹⁰) and Nb⁵⁺ (4d⁰).     

In-operando spectroscopic ellipsometry studies of IrO2 dynamic instabilities: Guide to in-situ growth of pyrochlore iridate thin films

The instability of iridium oxide at high temperature has long been a bottleneck for in growing pyrochlore iridate thin films in a vacuum chamber. To overcome this problem, we investigated the chemical instability of IrO₂ thin films, which are the simplest form of iridate, via in-operando spectroscopic ellipsometry (SE). We observed that IrO₂ thin films undergo IrO₂ dissociation and IrO₃ gas formation depending on the thermodynamic conditions. The chemical kinetics observations of IrO₂ were confirmed by ex-situ X-ray diffraction and atomic force microscopy. SE experimental data were compared with models used to describe the evolution of the two chemical reactions. Real-time in-operando SE analysis based on the Maxwell Garnett theory yielded a precise IrO₂ dissociation speed for the given thermodynamic conditions. Moreover, the real-time in-operando SE technique allowed us to observe the phase transition from solid IrO₂ to gaseous IrO₃. This study on the chemical instability of IrO₂ at high temperature affords insights into a new method for in-situ pyrochlore iridate and other iridates thin-film growth.     

Structural and impedance spectroscopy study of Samarium modified Barium Zirconium Titanate ceramic prepared by mechanochemical route

Samarium modified Barium Zirconium Titanate (BZT) ceramics with general formula [Ba_1−xSm_2x/3](Zr_0.05Ti_0.95O₃) [x = 0, 0.01, 0.02, 0.03 and 0.04] have been prepared by high energy ball milling. The Rietveld refinement of BaZr_0.05Ti_0.95O₃ (BZT) shows a single phase tetragonal symmetry with space group P4mmm and TEM micrograph shows that the crystalline size is in the submicron range. X-ray diffraction (XRD) patterns confirm that no phase change occurs with the addition of Samarium in BZT upto x ≤ 0.03 and a small pyrochlore phase exists at x = 0.04. The complex impedance (Nyquist) plots display a single semicircle highlighting the influence of grain resistance on the electrical behavior. Negative temperature coefficient of resistance behavior is observed in all compositions. The activation energy calculated from Z″ and DC conductivity confirms that the oxygen vacancies play an important role in the conduction mechanism.     

Structure and dehydration of the pyrochlore system NaW2−yMoyO6+δ·nH2−zO between 10 and 675 K

The temperature dependence of the structure of the pyrochlore NaW_2−yMo_yO_6+δ·nH_2−zO has been investigated using a variety of diffraction and spectroscopic methods. The positions of OH⁻/H₂O molecules in the structure have been determined. Increases in temperature induce small lattice parameter changes, which are thought to result from movement of the H₂O molecules in the pyrochlore lattice.     

Study of the KNO<Subscript>3</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> system by differential scanning calorimetry

The structural and the thermodynamic properties of potassium nitrate KNO₃ and its composites with nanosized aluminum oxide Al₂O₃ have been studied by differential scanning calorimetry. It has been found that an amorphous phase forms in composites (1–x)KNO_3–xAl₂O₃. The thermal effect corresponding to this phase has been observed at 316°C. It has been found that the phase transition heats of potassium nitrate decreased as the aluminum oxide fraction increased.     

Microstructure of laser melted Al18B4O33w/2024Al composite

The microstructure of a laser treated Al₁₈B₄O₃₃w/2024Al composite has been investigated using transmission electron microscope (TEM), low-angle (glancing angle) X-ray diffraction (XRD) techniques. Various surface microstructures were observed in the laser treated composite. The Al₁₈B₄O₃₃ whisker on the surface of the composite was decomposed during laser surface melting, various decomposition products were studied in the laser treated composite. Eutectic phases and the precipitation in the matrix of the composite with laser-treated were observed. The main phases detected in the molten zone were aluminum and decomposition products Al₂O₃. The effect of laser treatment on the hardness of the composite was also examined. A surface hardness of 400 Hv was noted.     

Interaction of optical phonons with magnons in orthorhombic crystals and the effect of magnetic field on structural phase transitions

The interaction of polar optical phonons with magnons in RMn₂O₅ manganates (R is a rare earth ion) has been studied in the approximation of collinear antiferromagnetic ordering of manganese sublattices. The effect of magnetic field on the structural phase transitions in these oxides has been analyzed.     

Characterization of novel cation-ordered compounds with fluorite and α-PbO2 related structures prepared by oxidation of Sn-Nb-O pyrochlore

Two cation-ordered phases were prepared by the oxidation of a pyrochlore phase as a precursor in the Sn-Nb-O system. One was a cation-ordered fluorite related phase, whose unit cell volume was eight times larger than that of the fluorite structure, similar to the κ-CeZrO₄ phase. The other was a cation-ordered α-PbO₂ phase, in which the ordered arrangement of cations was distinctly different from the well-known cation-ordered α-PbO₂ structures such as wolflamite and columbite. The chemical compositions of the phases, including valence states of cations, local structure and electronic structure near the energy band gap were studied. The compositions of the precursor and its oxidized phases were evaluated, respectively, to be Sn^II_1.62(Nb^V_1.86Sn^IV_0.14)O_6.55 and Sn^IV_0.81(Nb^V_0.93Sn^IV_0.07)O_4.085, i.e. Sn^IV_1.62(Nb^V_1.86Sn^IV_0.14)O_8.17, by TG-DTA and ICP analyses, ¹¹⁹Sn Mössbauer spectroscopy and X-ray photoemission spectroscopy. It was ascertained using IR and Raman spectroscopies that the structural framework of the cation-ordered fluorite related phase was close to that of the precursor pyrochlore phase, and the structural framework of the cation-ordered α-PbO₂ phase was distinct from that of the precursor pyrochlore. The Mössbauer parameters obtained showed a strong deviation of oxygen atoms contained in the SnO₈ polyhedron in the cation-ordered fluorite related phase from the cubic arrangement for the ideal fluorite related structure, and a lower site symmetry of Sn^IV in the cation-ordered α-PbO₂ than in rutile SnO₂. An increase in the energy band gap from ∼2.5 eV for the precursor pyrochlore to ∼3.5 eV for the oxidized phases was attributed to the vanishing of Sn 5s² lone-pair states upon oxidation of Sn^II in the precursor to Sn^IV in the oxidized phases.     

Effect of LaNiO3 buffer layers on the structure and electrical properties of sol–gel-derived Pb(Mg1/3Nb2/3)O3PbTiO3 thin films

Pb(Mg_1/3Nb_2/3)O₃PbTiO₃ (PMNT) thin films on Pt/TiO₂/SiO₂/Si substrates with and without a LaNiO₃ (LNO) buffer layer have been prepared using a sol–gel method. Structures and electrical properties of these two films have been investigated and compared. Highly (111)-oriented PMNT thin films with a certain amount of pyrochlore phase are obtained on bare Pt electrodes. On the contrary, (100)-oriented PMNT thin films with pure perovskite phase are formed on Pt electrodes with a LNO buffer layer. Cracks are found in the former but not in the latter. The dielectric constant of PMNT thin films on LNO-buffer Pt electrodes is larger than that on bare Pt electrodes. A great lowering of the leakage current is observed in the films with a LNO buffer layer. The improvement in the electrical properties is attributed to both the elimination of cracks and the suppression of pyrochlore phase in the films. PACS 77.84.Dy; 77.80.-e; 77.22.Gm     

Bismuth zinc niobate (Bi1.5ZnNb1.5O7) ceramics derived from metallo-organic decomposition precursor solution

The preparation, microstructure development and dielectric properties of Bi_1.5ZnNb_1.5O₇ pyrochlore ceramics by metallo-organic decomposition (MOD) route are reported. Homogeneous precalcined ceramic powders of 13-36 nm crystallite size were obtained at temperatures ranging from 500 to 700 °C. The thermal decomposition/oxidation of the gelled precursor solution was chemically analyzed, TG/DTA, XRD, and SEM, led to the formation of a pure cubic pyrochlore phase with a stoichiometry close to Bi_1.5ZnNb_1.5O₇ which begins to form at 500 °C. The metallo-organic precursor synthesis method, where Bi, Zn and Nb ions are chelated to form metal complexes, allows the control of Bi/Zn/Nb stoichiometric ratio on a molecular scale leading to the rapid formation of bismuth zinc niobate (Bi_1.5ZnNb_1.5O₇) ceramic fine powders with pure pyrochlore structure. The powders were pressed into pellets and can be sintered at temperatures as low as 800-1000 °C. Fine crystalline ceramics with the grain size in the range of 200-500 nm have been obtained at the sintering temperature of 800 °C. The dielectric properties in high frequency to microwave range were measured and discussed.