Ruddlesden-Popper faults in LaNiO3/LaAlO3 superlattices

Scanning transmission electron microscopy in combination with electron energy-loss spectroscopy is used to study LaNiO3/LaAlO3 superlattices grown on (La,Sr)AlO4 with varying single-layer thicknesses which are known to control their electronic properties. The microstructure of the films is investigated on the atomic level and the role of observed defects is discussed in the context of the different properties. Two types of Ruddlesden-Popper faults are found which are either two or three dimensional. The common planar Ruddlesden-Popper fault is induced by steps on the substrate surface. In contrast, the three-dimensionally arranged Ruddlesden-Popper fault, whose size is in the nanometer range, is caused by the formation of local stacking faults during film growth. Furthermore, the interfaces of the superlattices are found to show different sharpness, but the microstructure does not depend substantially on the single-layer thickness.Comment: 14 pages, 6 figure

Local stabilisation of polar order at charged antiphase boundaries in antiferroelectric (Bi_0.85Nd_0.15)(Ti_0.1Fe_0.9)O₃

Observation of an unusual, negatively-charged antiphase boundary in (Bi<sub>0.85</sub>Nd<sub>0.15</sub>)(Ti<sub>0.1</sub>Fe<sub>0.9</sub>)O<sub>3</sub> is reported. Aberration corrected scanning transmission electron microscopy is used to establish the full three dimensional structure of this boundary including O-ion positions to ~ ± 10 pm. The charged antiphase boundary stabilises tetragonally distorted regions with a strong polar ordering to either side of the boundary, with a characteristic length scale determined by the excess charge trapped at the boundary. Far away from the boundary the crystal relaxes into the well-known Nd-stabilised antiferroelectric phase

Single-atom vibrational spectroscopy in the scanning transmission electron microscope

Vibrational spectroscopy can achieve high energy resolution, but spatial resolution of unperturbed vibrations is more difficult to realize. Hage et al. show that a single-atom impurity in a solid (a silicon atom in graphene) can give rise to distinctive localized vibrational signatures. They used high-resolution electron energy-loss spectroscopy in a scanning transmission electron microscope to detect this signal. An experimental geometry was chosen that reduced the relative elastic scattering contribution, and repeated scanning near the silicon impurity enhanced the signal. The experimental vibration frequencies are in agreement with ab initio calculations.Science, this issue p. 1124Single-atom impurities and other atomic-scale defects can notably alter the local vibrational responses of solids and, ultimately, their macroscopic properties. Using high-resolution electron energy-loss spectroscopy in the electron microscope, we show that a single substitutional silicon impurity in graphene induces a characteristic, localized modification of the vibrational response. Extensive ab initio calculations reveal that the measured spectroscopic signature arises from defect-induced pseudo-localized phonon modestextemdashthat is, resonant states resulting from the hybridization of the defect modes and the bulk continuumtextemdashwith energies that can be directly matched to the experiments. This finding realizes the promise of vibrational spectroscopy in the electron microscope with single-atom sensitivity and has broad implications across the fields of physics, chemistry, and materials science

Electron Microscopy Reveals Structural and Chemical Changes at the Nanometer Scale in the Osteogenesis Imperfecta Murine Pathology

Alternations of collagen and mineral at the molecular level may have a significant impact on the strength and toughness of bone. In this study, scanning transmission electron microscopy (STEM) and electron energy-loss spectroscopy (EELS) were employed to study structural and compositional changes in bone pathology at nanometer spatial resolution. Tail tendon and femoral bone of osteogenesis imperfecta murine (oim, brittle bone disease) and wild type (WT) mice were compared to reveal defects in the architecture and chemistry of the collagen and collagen-mineral composite in the oim tissue at the molecular level. There were marked differences in the substructure and organization of the collagen fibrils in the oim tail tendon; some regions have clear fibril banding and organization, while in other regions fibrils are disorganized. Malformed collagen fibrils were loosely packed, often bent and devoid of banding pattern. In bone, differences were detected in the chemical composition of mineral in oim and WT. While mineral present in WT and oim bone exhibited the major characteristics of apatite, examination in EELS of the fine structure of the carbon K ionization edge revealed a significant variation in the presence of carbonate in different regions of bone. Variations have been also observed in the fine structure and peak intensities of the nitrogen K-edge. These alterations are suggestive of differences in the maturation of collagen nucleation sites or cross-links. Future studies will aim to establish the scale and impact of the modifications observed in oim tissues. The compositional and structural alterations at the molecular level cause deficiencies at larger length scales. Understanding the effect of molecular alterations to pathologic bone is critical to the design of effective therapeutics

Atomic-scale Interaction Dynamics in Few-layer Hexagonal Boron Nitride (h-BN)

Extended abstract of a paper presented at Microscopy and Microanalysis 2011 in Nashville, Tennessee, USA, August 7-August 11, 201

Atomically resolved chemical ordering at the nm-thick TiO precipitate/matrix interface in V-4Ti-4Cr alloy

We have used advanced analytical electron microscopy to characterise the local structure and chemistry at the interface between nm-thick TiO precipitates and the V-based matrix in a V-4Ti-4Cr alloy. Our results reveal the presence of an intergrowth between the fcc TiO and bcc vanadium structures, with a repeat lattice distance that equals 2.5 times the vanadium lattice parameter along the c-axis. Our atomic resolution analysis of the interface will impact the mechanistic understanding of its interaction with interstitials and radiation-induced lattice defects, and consequently trigger the development of improved alloy structures with interfaces engineered for enhanced radiation tolerance

Element-Specific Depth Profile of Magnetism and Stoichiometry at the La0.67Sr0.33MnO3/BiFeO3 Interface

Depth-sensitive magnetic, structural and chemical characterization is important in the understanding and optimization of novel physical phenomena emerging at interfaces of transition metal oxide heterostructures. In a simultaneous approach we have used polarized neutron and resonant X-ray reflectometry to determine the magnetic profile across atomically sharp interfaces of ferromagnetic La0.67Sr0.33MnO3 / multiferroic BiFeO3 bi-layers with sub-nanometer resolution. In particular, the X-ray resonant magnetic reflectivity measurements at the Fe and Mn resonance edges allowed us to determine the element specific depth profile of the ferromagnetic moments in both the La0.67Sr0.33MnO3 and BiFeO3 layers. Our measurements indicate a magnetically diluted interface layer within the La0.67Sr0.33MnO3 layer, in contrast to previous observations on inversely deposited layers. Additional resonant X-ray reflection measurements indicate a region of an altered Mn- and O-content at the interface, with a thickness matching that of the magnetic diluted layer, as origin of the reduction of the magnetic moment.Comment: 13 pages, 4 figures, supplemental material include

Interfacial Origin of the Magnetisation Suppression of Thin Film Yttrium Iron Garnet

Yttrium iron garnet has a very high Verdet constant, is transparent in the infrared and is an insulating ferrimagnet leading to its use in optical and magneto-optical applications. Its high Q-factor has been exploited to make resonators and filters in microwave devices, but it also has the lowest magnetic damping of any known material. In this article we describe the structural and magnetic properties of single crystal thin-film YIG where the temperature dependence of the magnetisation reveals a decrease in the low temperature region. In order to understand this complex material we bring a large number of structural and magnetic techniques to bear on the same samples. Through a comprehensive analysis we show that at the substrate -YIG interface, an interdiffusion zone of only 4 - 6nm exists. Due to the interdiffusion of Y from the YIG and Gd from the substrate, an addition magnetic layer is formed at the interface whose properties are crucially important in samples with a thickness of YIG less than 200nm