Microstructural, dielectric, pyroelectric and ferroelectric studies on partially grain-oriented SrBi2Ta2O9 ceramics

Partially grain-oriented (48%) ceramics of strontium bismuth tantalate (SrBi2Ta2O9) have been fabricated via conventional sintering. The grain-orientation factor of the ceramics was determined, as a function of both the sintering temperature and duration of sintering using X-ray powder diffraction (XRD) techniques. Variations in microstructural features (from acircular to plate like morphology) as a function of sintering temperature of the pellets were monitored by Scanning Electron Microscopy (SEM). The dielectric constant and loss measurements as functions of both frequency and temperature have been carried out along the directions parallel and perpendicular to the pressing axis. The anisotropy (epsilon(rn)/epsilon(rp)) associated was found to be 2.21. The effective dielectric constant of the samples with varying porosity was predicted using different dielectric mixture formulae. The grain boundary and grain interior contributions to the dielectric properties were rationalized using the impedance spectroscopy. The pyroelectric coefficient for strontium bismuth tantalate ceramic was determined along the parallel and perpendicular directions to the pressing axis and found to be -23 muC/m(2)K and -71 muC/m(2)K, respectively at 300 K. The ferroelectric properties of these partially grain-oriented ceramics are superior in the direction perpendicular to the pressing axis to that in the parallel direction.

Transmission electron microscopy study of domain structures in ferroelectric SrBi2Nb2O9 ceramics

A transmission electron microscopy study has been carried out on the domain structures of SrBi2Nb2O9 (SBN) ferroelectric ceramics which belong to the Aurivillius family of bismuth layered perovskite oxides. SBN is a potential candidate for Ferroelectric Random access memory (FeRAM) applications. The 90° ferroelectric domains and antiphase boundaries (APBs) were identified with dark field imaging techniques using different superlattice reflections which arise as a consequence of octahedral rotations and cationic shifts. The 90° domain walls are irregular in shape without any faceting. The antiphase boundaries are less dense compared to that of SrBi2Ta2O9(SBT). The electron microscopy observations are correlated with the polarization fatigue nature of the ceramic where the domain structures possibly play a key role in the fatigue- free behavior of the Aurivillius family of ferroelectric oxides.

Growth and Characterization Studies of ABi2ta2o9 (A = Ba, Sr and Ca) Ferroelectric Thin Films

Thin films of ferroelectric ABi2Ta2O9 bismuth-layered structure, where A = Ba, Sr and Ca, were prepared by pulsed laser deposition technique on Pt/TiO2/SiO2/Si(100) substrates. The influence of substrate temperature between 500 to 750°C, and oxygen partial pressure 100-300 mTorr, on the structural and electrical properties of the films was investigated. The films deposited above 650°C substrate temperature showed complete Aurivillius layered structure. Films annealed at 750°C for 1h in oxygen atmosphere have exhibited better electrical properties. Atomic force microscopy study of surface topography shows that the films grown at lower temperature has smaller grains and higher surface roughness. This paper discusses the pronounced influence of A-site cation substitution on the structural and ferroelectric properties with the aid of Raman spectroscopy, X-ray diffraction and electrical properties. The degradation of ferroelectric properties with Ba and Ca substitution at A-sites is attributed to the higher structural distortion caused by changing tolerance factor. A systematic proportionate variation of coercive field is attributed to electronegativity difference of A-site cations.

Growth and ferroelectric properties of Bi2VO5.5 thin films with metallic LaNiO3 electrodes

Novel ferroelectric bismuth vanadate, Bi2VO5.5 (BVO), thin films have been grown between lattice matched metallic LaNiO3 (LNO) layers deposited on SrTiO3 (STO) by the pulsed laser deposition technique. LNO/BVO/LNO/STO and Au/BVO/LNO/STO trilayer structures exhibited c‐oriented (001) growth of BVO. LNO has been found to be a good metallic electrode with sheet resistance ∼20 Ω in addition to aiding c‐axis oriented BVO growth. The dielectric constant, ϵr of LNO/BVO/LNO/STO, at 300 K was about 12. However, when an Au electrode was used on top of BVO/LNO/STO film, it showed a significant improvement in the dielectric constant (ϵr=123). The ferroelectric properties of BVO thin films have been confirmed by hysteresis behavior with a remnant polarization, Pr=4.6×10−8 C/cm2 and coercive field, Ec=23 kV/cm at 300 K.

Relaxor characteristics of layered Ba1-(3/2)xLaxBi2Nb2O9 ceramics

Barium lanthanum bismuth niobate Ba1−(3/2)xLaxBi2Nb2O9 (x = 0, 0.05, 0.1, and 0.15) powders have been prepared via solid state reaction route. The monophasic layered perovskite nature of each composition of these was confirmed by x-ray diffraction studies. A continuous decrease in the lattice parameter c of parent BaBi2Nb2O9 with increase in La3+ doping level was noteworthy. A decrease in dielectric constant maximum (εm), a shift in dielectric anomaly to lower temperatures (from 488 to 382 K), and an increase in the diffuseness (γ) (from 1.58 to 1.84) of dielectric anomaly were encountered on increasing x from 0 to 0.15. Vogel-Fulcher analyses showed a decrease in freezing temperature (Tf) (from 157 to 40 K) and an increase in the activation energy (0.53 to 1.12 eV) for frequency dispersion with increase in La3+ content. A downward shift in the peak position of the pyroelectric coefficient with increasing La3+ doping level was observed. The observed changes in the above physical properties were attributed to the increase in A-site chemical heterogeneity as a result of aliovalent La3+ doping on Ba2+ sites and associated A-site vacancy formation.

Structural and dielectric characteristics of Bi2O3-TiO2-SrB4O7 glasses

Glasses of the composition 0.20 Bi2O3 - 0.30 TiO2 - 0.50 SrB4O7 and 0.30 Bi2O3 - 0.45 TiO2 - 0.25 SrB4O7 have been fabricated by conventional glass processing technique. These glasses have been characterized using X-ray powder diffraction (XRD), differential thermal analysis (DTA) and high resolution transmission electron microscopy (HRTEM). The frequency response of the dielectric constant and the loss tangent of these glasses has been studied. The formation of the crystalline bismuth titanate, Bi4Ti3O12 (BiT) phase in the heat treated samples has been confirmed by XRD and HRTEM studies. The measured ET Of the glass-ceramics are found to be in good agreement with those predicted by the logarithmic mixture rule. Optical second harmonic generation (SHG) at 1064 nm has been observed in the heat treated samples and is attributed to the formation of crystalline Bi4Ti3O12 (BiT) phase in the SrB4O7 (SBO) matrix.

Photoluminescence study of mixed doped Ge-Se-In-Bi glasses

Photoluminescence studies, carried out using the Fourier Transform method rather than the conventional monochromator-dispersion method,are reported on glassy samples of indium-bismuth mixed doped Ge (10) Se(90-x-y) In (x) Bi (y) system (x,y = 5,10). The amorphous Bi2Se3 is found to be n-type like the crystalline counterpart. The possible contributions from microscopic cluster-level phase separation of Bi2Se3 and from the defects to the change in conductivity from p- to n- typein this system is discussed. The similar situation in related systems is also pointed out.

Synthesis of BiFeO by carbonate precipitation

Magnetoelectric multiferroic BiFeO3 (BFO) was synthesized by a simple carbonate precipitation technique of metal nitrate solutions. X-ray powder diffraction and thermo-gravimetric analysis (TGA) revealed that the precipitate consists of an intimate mixture of crystalline bismuth carbonate and an amorphous hydroxide of iron. The precipitate yielded BiFeO3 at an optimal calcination temperature of similar to 560A degrees C. Energy dispersive X-ray (EDX) analysis showed 1:1 ratio between Bi and Fe in the oxide. X-ray photoelectron spectroscopy (XPS) studies confirmed that Fe to be in +3 oxidation states both in the precipitated powder and BiFeO3. The synthesized BFO exhibits a very weak ferromagnetic correlation at room temperature and the degree of which increases slightly on cooling down to 10 K suggesting alteration in the long range spatial modulation of the spins arrangement as compared to the bulk BiFeO3.

Nonlinear Refraction and Two-Photon Absorption in Dense 2Bi(2)O(3)-B2O3 Glasses

High density transparent glasses (7.86 g/cc) were fabricated in the 2Bi(2)O(3)-B2O3 (BBO) system. Optical band gap of the obtained glasses was found to be 2.6eV. The refractive index measured for these glasses was 2.25 +/- 0.05 at lambda=543 nm. Nonlinear refraction and absorption studies were carried out on the BBO glasses using z-scan technique a lambda=532 nm of 10 ns pulse width. The nonlinear refractive index obtained was n(2)=12.1x10(-14) cm(2)/W and nonlinear absorption coefficient was beta=15.2 cm/GW. The n(2) and beta values of the BBO glasses were large compared to the other reported high index bismuth based oxide glass systems in the literature. These were attributed to the high density, high linear refractive index, low band gap and two photon absorption associated with these glasses. The electronic origin of large nonlinearities was discussed based on bond-orbital theory.

Raman & Infrared Study of Bi Filled Co4Sb12

CoSb3 skutterudites are established thermoelectric materials in the 500-800K temperature range. Undoped and Bi filled CoSb3 samples were synthesized by induction melting-annealing process and phase confirmation done by X-Ray diffraction. The role of bismuth as a filler in CoSb3 was investigated by Raman and far infrared reflectance study. It was found that bismuth strengthens Sb vibrations, and can potentially scatter Sb related acoustic phonons effectively. As a result substantial reduction in thermal conductivity may be possible with proper control of Bi filling.

Raman scattering, microstructural and dielectric studies on Ba1-xCaxBi4Ti4O15 ceramics

Polycrystalline powders of Ba1-xCaxBi4Ti4O15 (where x = 0, 0.25, 0.50, 0.75 and 1) were prepared via the conventional solid-state reaction route. X-ray diffraction (XRD) and Raman scattering techniques have been employed to probe into the structural changes on changing x. XRD analyses confirmed the formation of monophasic bismuth layered structure of all the above compositions with an increase in orthorhombic distortion with increase in x. Raman spectra revealed a redshift in A(1g) peak and an increase in the B-2g/B-3g splitting with increasing Ca content. The average grain size was found to increase with increasing x. The temperature of the maximum dielectric constant (T-m) increased linearly with increasing Ca-content whereas the diffuseness of the phase transition was found to decrease with the end member CaBi4Ti4O15 showing a frequency independent sharp phase transition around 1048 K. Ca doping resulted in a decrease in the remnant polarization and an increase in the coercive field. Ba0.75Ca0.25Bi4Ti4O15 ceramics showed an enhanced piezoelectric coefficient d(33) of 15 pC N-1 at room temperature. Low values of dielectric losses and tunability of temperature coefficient of dielectric constant (tau(epsilon)) in the present solid-solution suggest that these compounds can be of potential use in microwave dielectrics at high temperatures. (C) 2012 Elsevier B.V. All rights reserved.

Fabrication of novel Ag3PO4/BiOBr heterojunction with high stability and enhanced visible-light-driven photocatalytic activity

Herein, we report a facile and effective method to enhance the photocatalytic activity of bismuth oxybromide (BiOBr) semiconductor through the fabrication of heterojunction with Ag3PO4. The as synthesized Ag3PO4/BiOBr microspheres were characterized with transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), X-ray diffraction (XRD) and UV-vis diffuse reflectance spectroscopy (DRS). The new Ag3PO4/BiOBr heterojunctions exhibited wide absorption in the visible-light region and compared to pure BiOBr and Ag3PO4 samples displayed exceptionally high photocatalytic activity for the degradation of typical organic pollutants such as Rhodamine B (RhB) and phenol. The optimal Ag/Bi weight ratio in Ag3PO4/BiOBr microsphere (AB7) was found to be 0.7. The enhanced photocatalytic activity was related to the efficient separation of electron-hole pairs derived from matching band potentials between BiOBr and Ag3PO4 which results into the generation of natural energy bias at heterojunction and subsequent transfer of photoinduced charge carriers. Moreover, the synthesized samples exhibited almost no loss of activity even after 6 recycling runs indicating their high photocatalytic stability. Considering the facile and environment friendly route for the synthesis of Ag3PO4/BiOBr hybrids with enhanced visible-light induced photocatalytic activity, it is possible to widely apply these hybrids in various fields such as waste water treatment. (C) 2015 Elsevier B.V. All rights reserved.

Exploring the origin of ultralow thermal conductivity in layered BiOCuSe

Using first-principles density functional theory calculations, a systematic study of the lattice dynamics and related (e.g., dielectric and anharmonic) properties of BiOCuSe (bismuth-copper oxyselenide), along with a comparison with its isostructural analog LaOCuSe, is performed to find the origin of the ultralow thermal conductivity. in BiOCuSe. From the marked differences in some of these properties of the two materials, the reasons why BiOCuSe is a better thermal insulator than LaOCuSe are elucidated. For this class of oxychalcogenide thermoelectrics, phonon frequencies with symmetries, characters, spectroscopic activities, displacement patterns, and pressure coefficients of different zone-center modes, dielectric constants, dynamical charges, and phonon and Gruneisen dispersions are also determined.

In Situ Crystallographic Probing on Ameliorating Effect of Sulfide Additives and Carbon Grafting in Iron Electrodes

Beneficial effects of carbon grafting into the iron active material for rechargeable alkaline-iron-electrodes with and without Bi2S3 additive is probed by in situ X-ray diffraction in conjunction with Extended X-ray Absorption Fine Structure (EXAFS) and electrochemistry. EXAFS data unravel that the composition of pristine active material (PAM) for iron electrodes comprises 87% of magnetite and 13% of alpha-iron while carbon-grafted active material comprises 60% of magnetite and 40% of alpha-iron. In situ XRD patterns are recorded using a specially designed electrochemical cell. XRD data reflect that magnetite present in PAM iron electrode, without bismuth sulfide additive, is not reduced during charging while PAM iron electrode with bismuth sulfide additive is partially reduced to alpha-Fe/Fe(OH)(2). Interestingly, carbon-grafted-iron electrodes with bismuth sulfide exhibit complete conversion of active material to alpha-Fe/Fe(OH)2. The ameliorating effect of carbon grafting is substantiated by kinetic parameters obtained from steady-state potentiostatic polarization and Tafel plots. The mechanism for iron-electrode charge - discharge reactions are discussed in the light of the potential - pH diagrams for Fe - H2O, S - H2O and FeSads - H2O systems and it is surmised that carbon grafting into iron active material promotes its electrochemical utilization. (C) The Author(s) 2015. Published by ECS. All rights reserved.

Pressure-induced phase transition in Bi2Se3 at 3 GPa: electronic topological transition or not?

In recent years, a low pressure transition around P similar to 3 GPa exhibited by the A(2)B(3)-type 3D topological insulators is attributed to an electronic topological transition (ETT) for which there is no direct evidence either from theory or experiments. We address this phase transition and other transitions at higher pressure in bismuth selenide (Bi2Se3) using Raman spectroscopy at pressure up to 26.2 GPa. We see clear Raman signatures of an isostructural phase transition at P similar to 2.4 GPa followed by structural transitions at similar to 10 GPa and 16 GPa. First-principles calculations reveal anomalously sharp changes in the structural parameters like the internal angle of the rhombohedral unit cell with a minimum in the c/a ratio near P similar to 3 GPa. While our calculations reveal the associated anomalies in vibrational frequencies and electronic bandgap, the calculated Z(2) invariant and Dirac conical surface electronic structure remain unchanged, showing that there is no change in the electronic topology at the lowest pressure transition.