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

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

Atomic-Scale Time-Resolved Imaging of Krypton Dimers, Chains and Transition to a One-Dimensional Gas

Single-atom dynamics of noble-gas elements have been investigated using time-resolved transmission electron microscopy (TEM), with direct observation providing for a deeper understanding of chemical bonding, reactivity, and states of matter at the nanoscale. We report on a nanoscale system consisting of endohedral fullerenes encapsulated within single-walled carbon nanotubes ((Kr@C60)@SWCNT), capable of the delivery and release of krypton atoms on-demand, via coalescence of host fullerene cages under the action of the electron beam (in situ) or heat (ex situ). The state and dynamics of Kr atoms were investigated by energy dispersive X-ray spectroscopy (EDS), electron energy loss spectroscopy (EELS), and X-ray photoelectron spectroscopy (XPS). Kr atom positions were measured precisely using aberration-corrected high-resolution TEM (AC-HRTEM), aberration-corrected scanning TEM (AC-STEM), and single-atom spectroscopic imaging (STEM-EELS). The electron beam drove the formation of 2Kr@C120 capsules, in which van der Waals Kr2 and transient covalent [Kr2]+ bonding states were identified. Thermal coalescence led to the formation of longer coalesced nested nanotubes containing more loosely bound Krn chains (n = 3–6). In some instances, delocalization of Kr atomic positions was confirmed by STEM analysis as the transition to a one-dimensional (1D) gas, as Kr atoms were constrained to only one degree of translational freedom within long, well-annealed, nested nanotubes. Such nested nanotube structures were investigated by Raman spectroscopy. This material represents a highly compressed and dimensionally constrained 1D gas stable under ambient conditions. Direct atomic-scale imaging has revealed elusive bonding states and a previously unseen 1D gaseous state of matter of this noble gas element, demonstrating TEM to be a powerful tool in the discovery of chemistry at the single-atom level