Absence of Morphotropic Phase Boundary Effects in BiFeO3-PbTiO3 Thin Films Grown via a Chemical Multilayer Deposition Method

Here, we report the unusual behaviour shown by the (BiFeO3)1-x-(PbTiO3)x (BF-xPT) films prepared using a multilayer deposition approach by chemical solution deposition method. Thin film samples of various compositions were prepared by depositing several bilayers of BF and PT precursors by varying the BF or PT layer thicknesses. X-ray diffraction showed that final samples of all compositions show mixing of the two compounds resulting in a single phase mixture, also confirmed by transmission electron microscopy. In contrast to bulk equilibrium compositions, our samples show a monoclinic (MA type) structure suggesting disappearance of morphotropic phase boundary (MPB) about x = 0.30 as observed in the bulk. This is accompanied by the lack of any enhancement of remnant polarization at MPB as shown by the ferroelectric measurements. Magnetic measurements show that the magnetization of the samples increases with increasing BF content. Significant magnetization of the samples indicates melting of spin spirals in the BF-xPT arising from random distribution of iron atoms across the film. Absence of Fe2+ ions in the films was corroborated by X-ray photoelectron spectroscopy measurements. The results illustrate that used thin film processing methodology significantly changes the structural evolution in contrast to predictions from the equilibrium phase diagram as well as modify the functional characteristics of BP-xPT system dramatically.Comment: 15 pages, 6 figure

Preparation, structural, dielectric and magnetic properties of LaFeO3-PbTiO3 solid solutions

Solid solutions of (1-x)LaFeO3-(x)PbTiO3 (0<x<1) have been prepared by conventional solid-state reaction. These complex perovskites have been studied by means of X-ray (XRPD) and neutron powder (NPD) diffraction, complemented with dielectric, magnetic, heat capacity and M\"ossbauer measurements. Complete solubility in the perovskite series was demonstrated. The NPD and XRPD patterns were successfully refined as orthorhombic (x \leq 0.7) and tetragonal (x \geq 0.8). A composition-driven phase transformation occurs within the interval 0.7<x<0.8. The samples with x<0.5 showed evidence of long-range magnetic ordering with an G-type antiferromagnetic arrangement of the magnetic moments of the Fe3+ cations in the B-site with propagation vector k = (0,0,0). Based on the obtained experimental data, a combined structural and magnetic phase diagram has been constructed. The factors governing the structural, dielectric and magnetic properties of (1-x) LaFeO3 - (x)PbTiO3 solid solutions are discussed, as well as their possible multiferroicity.Comment: 33 pages, 15 figure

Spatial and temporal operation of the Scotia Sea ecosystem: a review of large-scale links in a krill centred food web

The Scotia Sea ecosystem is a major component of the circumpolar Southern Ocean system, where productivity and predator demand for prey are high. The eastward-flowing Antarctic Circumpolar Current (ACC) and waters from the Weddell–Scotia Confluence dominate the physics of the Scotia Sea, leading to a strong advective flow, intense eddy activity and mixing. There is also strong seasonality, manifest by the changing irradiance and sea ice cover, which leads to shorter summers in the south. Summer phytoplankton blooms, which at times can cover an area of more than 0.5 million km2, probably result from the mixing of micronutrients into surface waters through the flow of the ACC over the Scotia Arc. This production is consumed by a range of species including Antarctic krill, which are the major prey item of large seabird and marine mammal populations. The flow of the ACC is steered north by the Scotia Arc, pushing polar water to lower latitudes, carrying with it krill during spring and summer, which subsidize food webs around South Georgia and the northern Scotia Arc. There is also marked interannual variability in winter sea ice distribution and sea surface temperatures that is linked to southern hemisphere-scale climate processes such as the El Niño–Southern Oscillation. This variation affects regional primary and secondary production and influences biogeochemical cycles. It also affects krill population dynamics and dispersal, which in turn impacts higher trophic level predator foraging, breeding performance and population dynamics. The ecosystem has also been highly perturbed as a result of harvesting over the last two centuries and significant ecological changes have also occurred in response to rapid regional warming during the second half of the twentieth century. This combination of historical perturbation and rapid regional change highlights that the Scotia Sea ecosystem is likely to show significant change over the next two to three decades, which may result in major ecological shifts