Maghemite-like regions at crossing of two antiphase boundaries in doped BiFeO3

We report the observation of a novel structure at the point where two antiphase boundaries cross in a doped bismuth ferrite of composition (Bi0.85Nd0.15)(Fe0.9Ti0.1)O0.3. The structure was investigated using a combination of high angle annular dark field imaging and electron energy loss spectroscopy spectrum imaging in the scanning transmission electron microscope. A three-dimensional model was constructed by combining the position and chemistry data with previous results and assuming octahedral coordination of all Fe and Ti atoms. The resulting structure shows some novel L shaped arrangements of iron columns, which are coordinated in a similar manner to FeO6 octahedra in maghemite. It is suggested that this may lead to local ferromagnetic orderings similar to those in maghemite

Novel nanorod precipitate formation in neodymium and titanium codoped bismuth ferrite

The discovery of unusual nanorod precipitates in bismuth ferrite doped with Nd and Ti is reported. The atomic structure and chemistry of the nanorods are determined using a combination of high angle annular dark field imaging, electron energy loss spectroscopy, and density functional calculations. It is found that the structure of the BiFeO3 matrix is strongly modified adjacent to the precipitates; the readiness of BiFeO3 to adopt different structural allotropes in turn explains why such a large axial ratio, uncommon in precipitates, is stabilized. In addition, a correlation is found between the alignment of the rods and the orientation of ferroelastic domains in the matrix, which is consistent with the system's attempt to minimize its internal strain. Density functional calculations indicate a finite density of electronic states at the Fermi energy within the rods, suggesting enhanced electrical conductivity along the rod axes, and motivating future investigations of nanorod functionalities

Petrographic and chemical characterization and carbon and nitrogen isotopic compositions of cometary IDPs and their GEMS amorphous silicates

GEMS (glass with embedded metal and sulfides) are the dominant carrier of amorphous silicates in anhydrous interplanetary dust particles (IDPs) and one of the most suitable materials to study early solar system processes. Amorphous silicates in 105 GEMS from eight IDPs were analyzed regarding texture and chemical composition to reassess GEMS formation theories and genetic relationships to amorphous silicate material in meteorites. Petrography of bulk IDPs was investigated to understand GEMS’ relationships to other IDP components. Furthermore, carbon and nitrogen isotopic compositions were measured. Nearly all GEMS are aggregates of several subgrains with variable amount of nanophase inclusions and different Mg- and Si-contents, while single GEMS are rare. The subgrains within aggregates are typically surrounded by one or more carbon rims with high density. The chemical compositions of GEMS amorphous silicates are subsolar for all major element/Si ratios but exhibit wide heterogeneity. This is not influenced by silicon oil from the capturing process of IDPs as assumed before, as a penetration of the silicon oil is excluded by high resolution EELS (electron energy loss spectroscopy) areal density maps of silicon. Furthermore, low Fe-content in GEMS amorphous silicates shows that these are not altered by aqueous activity on the parent body as it is the case for amorphous silicate material in primitive meteorites. The subsolar element/Si ratios and the wide chemical heterogeneity point to a non-equilibrium fractional condensation origin either in the early solar nebula or in a circumstellar environment and are not in agreement with homogenization via sputtering in the ISM. The close association with carbon around GEMS subgrains and as double-rims around GEMS aggregates argue for a multi-step aggregation after formation of the smallest GEMS subgrains in the ISM or the early solar nebula. Carbon acting as matrix material connecting GEMS and other IDP components has lower areal density as seen from carbon EELS areal density maps and isotopic anomalies varying at the nanometer scale, pointing to different origins and processing of materials to varying extent or at changing temperatures. To balance GEMS’ subsolar element/Si ratios, a supersolar component in IDPs was assumed to account for the overall chondritic composition of bulk IDPs. Nevertheless, our bulk IDP analyses revealed subsolar, but variable, element/Si ratios for complete particles as well, depending on type and amount of mineral phases in each particle. Pyroxenes in the investigated particles can occur as elongated euhedral crystals, but are overall rare. The dominant crystalline fraction in the investigated IDP samples are equilibrated aggregates (EAs) that show the same chemical compositions as GEMS, indicating that the EAs are recrystallized GEMS grains and formed after GEMS formation as secondary phases

Segregation of Yttrium at the Mg/MgO interface in an Mg-0.5Y Alloy

Interfacial segregation of selected elements can be exploited to manipulate the potency of solid substrates for heterogeneous nucleation, thus controlling the solidification process. As the native inclusions in Mg alloys, MgO acts as the nucleating substrate, but it has rarely been studied in terms of its interactions with alloying elements. In this work, investigations of yttrium (Y) segregation at interfaces between native MgO particles and Mg in an Mg-0.5Y alloy were carried out by state-of-the-art aberration-corrected scanning transmission electron microscopy (STEM) and associated spectroscopy. Experimental results show that native MgO particles in Mg-0.5Y possess two typical morphologies: truncated octahedron primarily faceted by {111}MgO and minorly by {100}MgO, and cubic shape with unique {100}MgO facets. Y atoms are found to segregate at both Mg/{111}MgO and Mg/{100}MgO interfaces, leading to the formation of two different 2-dimensional compounds (2DCs). The 2DC at the Mg/{111}MgO interface is identified as two atomic layers of a face-centered cubic Y2O3 phase in terms of crystal structure and chemistry, whilst it is an Mg(Y)-O monolayer at the Mg/{100}MgO interface, coherently matching with the terminating {100}MgO plane. Discussion is focused on the mechanisms underlying the formation of the 2DCs, their effects on the nucleation potency of MgO particles, and grain refinement. This work sheds light on how heterogeneous nucleation can be manipulated by altering the nucleation potency of a substrate through deliberately promoting elemental segregation of carefully chosen element(s)

Grain-Boundary Structural Relaxation in Sb2Se3{\mathrm{Sb}}_{2}{\mathrm{Se}}_{3} Thin-Film Photovoltaics

Grain boundaries play an important role in the efficiency of thin-film photovoltaics, where the absorber layer is invariably polycrystalline. Density-functional-theory simulations have previously identified a “self-healing” mechanism in Sb2Se3 that passivates the grain boundaries. During “self-healing,” extensive structural relaxation at the grain boundary removes the band-gap electronic defect states that give rise to high carrier recombination rates. In this work, lattice imaging in a transmission electron microscope is used to uncover evidence for the theoretically proposed structural relaxation in Sb2Se3. The strain measured along the [010] crystal direction is found to be dependent on the nature of the grain-boundary plane. For a (010) grain boundary, the strain and structural relaxation is minimal, since no covalent bonds are broken by termination of the grain. On the other hand, strains of up to approximately 4% extending approximately 2 nm into the grain interior are observed for a (041) grain boundary, where grain termination results in significant structural relaxation due to the ideal atomic coordination being disrupted. These results are consistent with theory and suggest that Sb2Se3 may have a high level of grain-boundary-defect tolerance

Bimetallic copper palladium nanorods: plasmonic properties and palladium content effects

Cu is an inexpensive alternative plasmonic metal with optical behaviour comparable to Au but with much poorer environmental stability. Alloying with a more stable metal can improve stability and add functionality, with potential effects on the plasmonic properties. Here we investigate the plasmonic behaviour of Cu nanorods and Cu–CuPd nanorods containing up to 46 mass percent Pd. Monochromated scanning transmission electron microscopy electron energy-loss spectroscopy first reveals the strong length dependence of multiple plasmonic modes in Cu nanorods, where the plasmon peaks redshift and narrow with increasing length. Next, we observe an increased damping (and increased linewidth) with increasing Pd content, accompanied by minimal frequency shift. These results are corroborated by and expanded upon with numerical simulations using the electron-driven discrete dipole approximation. This study indicates that adding Pd to nanostructures of Cu is a promising method to expand the scope of their plasmonic applications

The effect of substrate clamping on the paraelectric to antiferroelectric phase transition in Nd-doped BiFeO₃ thin films

Thin films were deposited on Pt/Ti/SiO₂/Si substrates using pulsed laser deposition from a target with a composition (Bi₀.₈₂₅Nd₀.₁₇₅Fe₀.₉₇Ti₀.₀₃O₃) with 5 mol% excess Bi₂O₃ within the antiferroelectric (AFE) region of the NdFeO₃-BiFeO₃ phase diagram. However, Raman spectroscopy and transmission electron microscopy (TEM) revealed that films consisted of a mosaic microstructure in which (AFE), ferroelectric (FE) and paraelectric (PE) phases coexisted. Variation in the spatial distribution of Nd is typically greater in bulk ceramics than in thin films and therefore, the absence of single phase AFE cannot be attributed to local changes in composition. Instead, it is proposed that clamping due to mismatch in thermal expansion coefficient with the substrate suppresses the large volume change associated with the PE-FE and PE-AFE transition in bulk and its absence in the thin film prevents an avalanche-like transition throughout grains, which in bulk sustains single phase AFE, irrespective of local deviations in the Nd concentration

High-spatial resolution functional chemistry of nitrogen compounds in the observed UK meteorite fall Winchcombe

Organic matter in extraterrestrial samples is a complex material that might have played an important role in the delivery of prebiotic molecules to the early Earth. We report here on the identification of nitrogen-containing compounds such as amino acids and N-heterocycles within the recent observed meteorite fall Winchcombe by high-spatial resolution spectroscopy techniques. Although nitrogen contents of Winchcombe organic matter are low (N/C ~ 1–3%), we were able to detect the presence of these compounds using a low-noise direct electron detector. These biologically relevant molecules have therefore been tentatively found within a fresh, minimally processed meteorite sample by high spatial resolution techniques conserving the overall petrographic context. Carbon functional chemistry investigations show that sizes of aromatic domains are small and that abundances of carboxylic functional groups are low. Our observations demonstrate that Winchcombe represents an important addition to the collection of carbonaceous chondrites and still preserves pristine extraterrestrial organic matter

Interface ferromagnetism and orbital reconstruction in BiFeO3- La0.7Sr0.3MnO3 heterostructures

We report the formation of a novel ferromagnetic state in the antiferromagnet BiFeO3 at the interface with La0.7Sr0.3MnO3. Using x-ray magnetic circular dichroism at Mn and Fe L2,3-edges, we discovered that the development of this ferromagnetic spin structure is strongly associated with the onset of a significant exchange bias. Our results demonstrate that the magnetic state is directly related with an electronic orbital reconstruction at the interface, which is supported by the linearly polarized x-ray absorption measurement at oxygen K-edge.Comment: 17 pages, 4 figures, PRL in pres