Aqueous Cold Sintering of Li-Based Compounds.

Aqueous cold sintering of two lithium-based compounds, the electrolyte Li6.25La3Zr2Al0.25O12 (LLZAO) and cathode material LiCoO2 (LCO), is reported. For LLZAO, a relative density of ∼87% was achieved, whereas LCO was sintered to ∼95% with 20 wt % LLZAO as a flux/binder. As-cold sintered LLZAO exhibited a low total conductivity (10-8 S/cm) attributed to an insulating grain boundary blocking layer of Li2CO3. The blocking layer was reduced with a post-annealing process or, more effectively, by replacing deionized water with 5 M LiCl during cold sintering to achieve a total conductivity of ∼3 × 10-5 S/cm (similar to the bulk conductivity). For LCO-LLZAO composites, scanning electron microscopy and X-ray computer tomography indicated a continuous LCO matrix with the LLZAO phase evenly distributed but isolated throughout the ceramics. [001] texturing during cold sintering resulted in an order of magnitude difference in electronic conductivity between directions perpendicular and parallel to the c-axis at room temperature. The electronic conductivity (∼10-2 S/cm) of cold sintered LCO-LLZAO ceramics at room temperature was comparable to that of single crystals and higher than those synthesized via either conventional sintering or hot pressing.

Multiple Local Symmetries Result in a Common Average Polar Axis in High-Strain BiFeO_{3}-Based Ceramics.

For the first time, the origin of large electrostrain in pseudocubic BiFeO_{3}-based ceramics is verified with direct structural evidence backed by appropriate simulations. We employ advanced structural and microstructural characterizations of BiFeO_{3}-based ceramics that exhibit large electrostrain (>0.4%) to reveal the existence of multiple, nanoscale local symmetries, dominantly tetragonal or orthorhombic, which have a common, averaged direction of polarization over larger, meso- or microscale regions. Phase-field simulations confirm the existence of local nanoscale symmetries, thereby providing a new vision for designing high-performance lead-free ceramics for high-strain actuators.

Dynamic tilting in perovskites.

A new computational analysis of tilt behaviour in perovskites is presented. This includes the development of a computational program - PALAMEDES - to extract tilt angles and the tilt phase from molecular dynamics simulations. The results are used to generate simulated selected-area electron and neutron diffraction patterns which are compared with experimental patterns for CaTiO3. The simulations not only reproduced all symmetrically allowed superlattice reflections associated with tilt but also showed local correlations that give rise to symmetrically forbidden reflections and the kinematic origin of diffuse scattering.

High oxide-ion conductivity in acceptor-doped Bi-based perovskites at modest doping levels.

A combination of impedance spectroscopy, time-of-flight secondary ion mass spectrometry and literature data are used to show that, (i) the bulk oxide ion conductivity of A-site, alkaline earth-doped BiFeO3 (BF) is independent of the ionic radius of the alkaline earth ion (Ca, Sr, Ba) and, (ii) despite very different A-site environments in (Na1/2Bi1/2)TiO3 and BF, similar high levels and optimisation of bulk oxide ion conductivity in these Bi-based tilted perovskites is achieved at modest acceptor doping levels of ∼1-10%. These results clearly demonstrate that optimisation of oxide ion conductivity in these materials requires concepts beyond a simple crystallochemical approach based on matching the ionic radii of acceptor dopant and host lattice ions.

Nanoscale Mapping of Bromide Segregation on the Cross Sections of Complex Hybrid Perovskite Photovoltaic Films Using Secondary Electron Hyperspectral Imaging in a Scanning Electron Microscope.

Mixed halide (I/Br) complex organic/inorganic hybrid perovskite materials have attracted much attention recently because of their excellent photovoltaic properties. Although it has been proposed that their stability is linked to the chemical inhomogeneity of I/Br, no direct proof has been offered to date. Here, we report a new method, secondary electron hyperspectral imaging (SEHI), which allows direct imaging of the local variation in Br concentration in mixed halide (I/Br) organic/inorganic hybrid perovskites on a nanometric scale. We confirm the presence of a nonuniform Br distribution with variation in concentration within the grain interiors and boundaries and demonstrate how SEHI in conjunction with low-voltage scanning electron microscopy can enhance the understanding of the fundamental physics and materials science of organic/inorganic hybrid photovoltaics, illustrating its potential for research and development in "real-world" applications.

Synthesis of Barium Titanate Using Deep Eutectic Solvents.

Novel synthetic routes to prepare functional oxides at lower temperatures are an increasingly important area of research. Many of these synthetic routes, however, use water as the solvent and rely on dissolution of the precursors, precluding their use with, for example, titanates. Here we present a low-cost solvent system as a means to rapidly create phase-pure ferroelectric barium titanate using a choline chloride-malonic acid deep eutectic solvent. This solvent is compatible with alkoxide precursors and allows for the rapid synthesis of nanoscale barium titanate powders at 950 °C. The phase and morphology were determined, along with investigation of the synthetic pathway, with the reaction proceeding via BaCl2 and TiO2 intermediates. The powders were also used to create sintered ceramics, which exhibit a permittivity maximum corresponding to a tetragonal-cubic transition at 112 °C, as opposed to the more conventional temperature of ∼120 °C. The lower-than-expected value for the ferro- to para-electric phase transition is likely due to undetectable levels of contaminants.

Synthesis of a 12R-type hexagonal perovskite solid solution Sr3NdNb(3-x)Ti(x)O(12-δ) and the influence of acceptor doping on electrical properties.

A solid solution forms for Sr3NdNb(3-x)Ti(x)O(12-δ) with approximate limits 0 ≤ x ≤ 0.06. The system crystallizes with a 12R-type hexagonal perovskite structure in the space group R3, as determined by neutron diffraction and selected area electron diffraction. The electrical properties of the end members have been investigated by impedance spectroscopy in the temperature range 550-800 °C under various gas atmospheres and as a function of oxygen and water-vapour partial pressure. Proton transport dominates under wet oxidising conditions in the temperature range 550-700 °C, as confirmed by the H(+)/D(+) isotope effect. Acceptor doping considerably enhances proton conductivity with a value of 3.3 × 10(-6) S cm(-1) for the bulk response of x = 0.06 at 700 °C in moistened air. The presence of a -» slope for both doped and undoped samples in the range 10(-19) ≤ pO2 ≤ 10(-8) atm at 900 °C indicates n-type transport under reducing conditions following the extrinsic model attributable to acceptor centres. The conductivity is essentially independent of pO2 at 600 °C under dry oxidising conditions, consistent with oxide-ion transport; a positive power-law dependence at higher temperature indicates extrinsic behaviour and a significant electron-hole contribution. The dielectric constant at RT of nominally stoichiometric Sr3NdNb3O12 is εr ∼ 37, with a moderately high quality factor of Q × f ∼ 16,400 GHz at fr ∼ 6.4 GHz. The temperature coefficient of resonant frequency of x = 0 is τf ∼ 12 ppm °C(-1), which lowers to -3 ppm °C(-1) for the Ti-doped phase x = 0.06.

A family of oxide ion conductors based on the ferroelectric perovskite Na0.5Bi0.5TiO3.

Oxide ion conductors find important technical applications in electrochemical devices such as solid-oxide fuel cells (SOFCs), oxygen separation membranes and sensors. Na0.5Bi0.5TiO3 (NBT) is a well-known lead-free piezoelectric material; however, it is often reported to possess high leakage conductivity that is problematic for its piezo- and ferroelectric applications. Here we report this high leakage to be oxide ion conduction due to Bi-deficiency and oxygen vacancies induced during materials processing. Mg-doping on the Ti-site increases the ionic conductivity to ~0.01 S cm(-1) at 600 °C, improves the electrolyte stability in reducing atmospheres and lowers the sintering temperature. This study not only demonstrates how to adjust the nominal NBT composition for dielectric-based applications, but also, more importantly, gives NBT-based materials an unexpected role as a completely new family of oxide ion conductors with potential applications in intermediate-temperature SOFCs and opens up a new direction to design oxide ion conductors in perovskite oxides.

Nanoscale electrical probing of heterogeneous ceramics: the case of giant permittivity calcium copper titanate (CaCu3Ti4O12).

Scanning Probe Microscopy with conductive tips has been used to image and study the dielectric properties of giant permittivity CaCu3Ti4O12 ceramics at the nanoscale. Since measurements are generally carried out on sections of a sample, particular attention has been devoted to possible artefacts due to surface imperfections, such as substantial surface roughness and/or contamination that can result in controversial interpretation, particularly at nanometric spatial dimensions. A reliable surface investigation has been carried out after the definition of both the physical and geometrical unbiased criteria to avoid any artefacts due to surface roughness and/or anomalous tip-sample contact variations. The presence of insulating grain boundaries and the measurement of a depletion layer at the grain-grain boundary interfaces unambiguously demonstrate the relevance of the Internal Barrier Layer Capacitor effect, among all the proposed physical mechanisms, to explain the giant dielectric behaviour. Such imaging provided a clear correlation between the macroscopic dielectric properties and the nanometric structure at the interfaces. Moreover, the "general criteria" for reliable nanoelectrical characterization as well as the related measurement resolution have been defined.

Enhanced oxide ion conductivity in stabilized delta-Bi2O3.

The substitution of Re into Bi2O3 allows stabilization of the delta-Bi2O3 structure by additional substitution of any lanthanide ion to give, for example, phases of composition Bi12.5La1.5ReO24.5. Some of these phases have been found to show exceptionally high oxide ion conductivity at low temperatures, ca 10-3 S cm-1 at 300 degrees C. The phases show a significant structural difference from other delta-Bi2O3 phases previously reported, with interstitial anion sites displaced further from the ideal fluorite position, (1/4,1/4,1/4).

EELS characterisation of bulk CaCu3Ti4O12 ceramics.

CaCu3Ti4O12 (CCTO) is a cubic perovskite phase and sintered ceramics exhibit high permittivity at room temperature. Electron energy-loss spectroscopy (EELS) and energy dispersive X-ray spectrometry (EDS) data have been collected from samples of CCTO to relate the observed electrical properties to the microstructure and chemistry on the nanoscale. CCTO ceramics were sintered for 24h at 1115 degrees C in air, giving a grain size of 50-300 microm. Ti L(2,3)-, Cu L(2,3)- and O K-edge EEL data were collected for bulk CCTO (within grain) and compared with well characterised Ti-oxides, CaTiO3 and BaTiO3 perovskites. The bulk metal L(2,3)-edge data for CCTO suggest that Cu is divalent and Ti is present as Ti4+. The O K-edge of CCTO shows increased near-edge structure (NES) compared to those of the simple perovskites.