Reduction-Induced Magnetic Behavior in LaFeO3-δ Thin Films.

The effect of oxygen reduction on the magnetic properties of LaFeO3-δ (LFO) thin films was studied to better understand the viability of LFO as a candidate for magnetoionic memory. Differences in the amount of oxygen lost by LFO and its magnetic behavior were observed in nominally identical LFO films grown on substrates prepared using different common methods. In an LFO film grown on as-received SrTiO3 (STO) substrate, the original perovskite film structure was preserved following reduction, and remnant magnetization was only seen at low temperatures. In a LFO film grown on annealed STO, the LFO lost significantly more oxygen and the microstructure decomposed into La- and Fe-rich regions with remnant magnetization that persisted up to room temperature. These results demonstrate an ability to access multiple, distinct magnetic states via oxygen reduction in the same starting material and suggest LFO may be a suitable materials platform for nonvolatile multistate memory.

Epitaxial antiperovskite/perovskite heterostructures for materials design.

Engineered heterostructures formed by complex oxide materials are a rich source of emergent phenomena and technological applications. In the quest for new functionality, a vastly unexplored avenue is interfacing oxide perovskites with materials having dissimilar crystallochemical properties. Here, we propose a unique class of heterointerfaces based on nitride antiperovskite and oxide perovskite materials as a previously unidentified direction for materials design. We demonstrate the fabrication of atomically sharp interfaces between nitride antiperovskite Mn3GaN and oxide perovskites (La0.3Sr0.7)(Al0.65Ta0.35)O3 and SrTiO3. Using atomic-resolution imaging/spectroscopic techniques and first-principles calculations, we determine the atomic-scale structure, composition, and bonding at the interface. The epitaxial antiperovskite/perovskite heterointerface is mediated by a coherent interfacial monolayer that interpolates between the two antistructures. We anticipate our results to be an important step for the development of functional antiperovskite/perovskite heterostructures, combining their unique characteristics such as topological properties for ultralow-power applications.

Epitaxial K0.5Na0.5NbO3 thin films by aqueous chemical solution deposition.

We report on an environmentally friendly and versatile aqueous chemical solution deposition route to epitaxial K0.5Na0.5NbO3 (KNN) thin films. The route is based on the spin coating of an aqueous solution of soluble precursors on SrTiO3 single crystal substrates followed by pyrolysis at 400°C and annealing at 800°C using rapid thermal processing. Strongly textured films with homogeneous thickness were obtained on three different crystallographic orientations of SrTiO3. Epitaxial films were obtained on (111) SrTiO3 substrates, while films consisting of an epitaxial layer close to the substrate followed by an oriented polycrystalline layer were obtained on (100) and (110) SrTiO3 substrates. A K2Nb4O11 secondary phase was observed on the surface of the thin films due to the evaporation of alkali species, while the use of an NaCl/KCl flux reduced the amount of the secondary phase. Ferroelectric behaviour of the films was investigated by PFM, and almost no dependence on the film crystallographic orientation was observed. The permittivity and loss tangent of the films with the NaCl/KCl flux were 870 and 0.04 (100-orientation) and 2250 and 0.025 (110-orientation), respectively, at 1 kHz.

Spatially Confined Spin Polarization and magnetic sublattice control in (La,Sr)MnO3-δ Thin Films by Oxygen Vacancy Ordering.

Perovskite oxides are known for their strong structure property coupling and functional properties such as ferromagntism, ferroelectricity and high temperature superconductivity. While the effect of ordered cation vacancies on functional properties have been much studied, the possibility of tuning the functionality through anion vacancy ordering has received much less attention. Oxygen vacancies in ferromagnetic La0.7Sr0.3MnO3-δ thin films have recently been shown to accumulate close to interfaces and form a brownmillerite structure (ABO2.5). This structure has alternating oxygen octahedral and tetrahedral layers along the stacking direction, making it a basis for a family of ordered anion defect controlled materials. We use density functional theory to study how structure and properties depend on oxygen stoichiometry, relying on a block-by-block approach by including additional octahedral layers in-between each tetrahedral layer. It is found that the magnetic and electronic structures follow the layers enforced by the ordered oxygen vacancies. This results in spatially confined electronic conduction in the octahedral layers, and decoupling of the magnetic sub-lattices in the octahedral and tetrahedral layers. These results demonstrate that anion defect engineering is a promising tool to tune the properties of functional oxides, adding a new avenue for developing functional oxide device technology.

Atomap: a new software tool for the automated analysis of atomic resolution images using two-dimensional Gaussian fitting.

Scanning transmission electron microscopy (STEM) data with atomic resolution can contain a large amount of information about the structure of a crystalline material. Often, this information is hard to extract, due to the large number of atomic columns and large differences in intensity from sublattices consisting of different elements. In this work, we present a free and open source software tool for analysing both the position and shapes of atomic columns in STEM-images, using 2-D elliptical Gaussian distributions. The software is tested on variants of the perovskite oxide structure. By first fitting the most intense atomic columns and then subtracting them, information on all the projected sublattices can be obtained. From this, we can extract changes in the lattice parameters and shape of A-cation columns from annular dark field images of perovskite oxide heterostructures. Using annular bright field images, shifts in oxygen column positions are also quantified in the same heterostructure. The precision of determining the position of atomic columns is compared between STEM data acquired using standard acquisition, and STEM-images obtained as an image stack averaged after using non-rigid registration.

Interstitial oxygen as a source of p-type conductivity in hexagonal manganites.

Hexagonal manganites, h-RMnO3 (R=Sc, Y, Ho-Lu), have been intensively studied for their multiferroic properties, magnetoelectric coupling, topological defects and electrically conducting domain walls. Although point defects strongly affect the conductivity of transition metal oxides, the defect chemistry of h-RMnO3 has received little attention. We use a combination of experiments and first principles electronic structure calculations to elucidate the effect of interstitial oxygen anions, Oi, on the electrical and structural properties of h-YMnO3. Enthalpy stabilized interstitial oxygen anions are shown to be the main source of p-type electronic conductivity, without reducing the spontaneous ferroelectric polarization. A low energy barrier interstitialcy mechanism is inferred from Density Functional Theory calculations to be the microscopic migration path of Oi. Since the Oi content governs the concentration of charge carrier holes, controlling the thermal and atmospheric history provides a simple and fully reversible way of tuning the electrical properties of h-RMnO3.

Assessing electron beam sensitivity for SrTiO3 and La0.7Sr0.3MnO3 using electron energy loss spectroscopy.

Thresholds for beam damage have been assessed for La0.7Sr0.3MnO3 and SrTiO3 as a function of electron probe current and exposure time at 80 and 200kV acceleration voltage. The materials were exposed to an intense electron probe by aberration corrected scanning transmission electron microscopy (STEM) with simultaneous acquisition of electron energy loss spectroscopy (EELS) data. Electron beam damage was identified by changes of the core loss fine structure after quantification by a refined and improved model based approach. At 200kV acceleration voltage, damage in SrTiO3 was identified by changes both in the EEL fine structure and by contrast changes in the STEM images. However, the changes in the STEM image contrast as introduced by minor damage can be difficult to detect under several common experimental conditions. No damage was observed in SrTiO3 at 80kV acceleration voltage, independent of probe current and exposure time. In La0.7Sr0.3MnO3, beam damage was observed at both 80 and 200kV acceleration voltages. This damage was observed by large changes in the EEL fine structure, but not by any detectable changes in the STEM images. The typical method to validate if damage has been introduced during acquisitions is to compare STEM images prior to and after spectroscopy. Quantifications in this work show that this method possibly can result in misinterpretation of beam damage as changes of material properties.

Spin-flop coupling and exchange bias in embedded complex oxide micromagnets.

The magnetic domains of embedded micromagnets with 2 µm×2 µm dimensions defined in epitaxial La0.7Sr0.3MnO3 (LSMO) thin films and LaFeO3/LSMO bilayers were investigated using soft x-ray magnetic microscopy. Square micromagnets aligned with their edges parallel to the easy axes of LSMO provide an ideal experimental geometry for probing the influence of interface exchange coupling on the magnetic domain patterns. The observation of unique domain patterns not reported for ferromagnetic metal microstructures, namely divergent antiferromagnetic vortex domains and "Z"-type domains, suggests the simultaneous presence of spin-flop coupling and local exchange bias in this system.

Crossover from spin-flop coupling to collinear spin alignment in antiferromagnetic/ferromagnetic nanostructures.

The technologically important exchange coupling in antiferromagnetic/ferromagnetic bilayers is investigated for embedded nanostructures defined in a LaFeO(3)/La(0.7)Sr(0.3)MnO(3) bilayer. Exploiting the element specificity of soft X-ray spectromicroscopy, we selectively probe the magnetic order in the two layers. A transition from perpendicular to parallel spin alignment is observed for these nanostructures, dependent on size and crystalline orientation. The results show that shape-induced anisotropy in the antiferromagnet can override the interface exchange coupling in spin-flop coupled nanostructures.

Antiferromagnetic domain reconfiguration in embedded LaFeO3 thin film nanostructures.

Using photoemission electron microscopy in combination with X-ray magnetic linear dichroism, we report reconfiguration upon nanostructuring of the antiferromagnetic domain structure in epitaxial LaFeO3 thin films. Antiferromagnetic (AFM) nanoislands were synthesized using a dedicated process, devised to define nanostructures with magnetic order embedded in a paramagnetic matrix. Significant impact on the AFM domain configuration was observed. Extended domains were found to form along edges parallel to the in-plane <100> crystalline axes of the cubic substrate, with their AFM spin axis parallel to the edge. No such edge-imposed domain configuration was found for nanoislands defined with the edges at 45° with the in-plane crystalline axes. Epitaxial constraints on the film crystalline structure appear to play an important role in the formation of the edge-bound extended AFM domains. The data indicate a magnetostatic origin of this domain reconfiguration.

Comparison of TEM specimen preparation of perovskite thin films by tripod polishing and conventional ion milling.

In this article, the effects of the transmission electron microscopy (TEM) specimen preparation techniques, such as ion milling and tripod polishing on perovskite oxides for high-resolution TEM investigation, are compared. Conventional and liquid nitrogen cooled ion milling induce a new domain orientation in thin films of SrRuO(3) and LaFeO(3) grown on (001)-oriented SrTiO(3) substrates. This is not observed in tripod-polished specimens. Different ion milling rates for thin films and substrates in cross-section specimens lead to artefacts in the interface region, degrading the specimen quality. This is illustrated by SrRuO(3) and PbTiO(3) thin films grown on (001)-oriented SrTiO(3). By applying tripod polishing and gentle low-angle, low-energy ion milling while cooling the sample, the effects from specimen preparation are reduced resulting in higher quality of the TEM study. In the process of making face-to-face cross-section specimens by tripod polishing, it is crucial that the glue layer attaching the slabs of material is very thin (<50 nm).

PbTiO(3) nanorod arrays grown by self-assembly of nanocrystals.

Arrays of ferroelectric lead titanate (PbTiO(3)) nanorods have been grown on a substrate by a novel template-free method. Hydrothermal treatment of an amorphous PbTiO(3) precursor in the presence of a surfactant and PbTiO(3) or SrTiO(3) substrates resulted in the growth of PbTiO(3) nanorod arrays aligned perpendicular to the substrate surface. Two steps in the growth mechanism were demonstrated: first an epitaxial layer was formed on the substrate; this was followed by self-assembly of nanocrystals forming a mesocrystal layer which matured into arrays of PbTiO(3) nanorods.