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The choice of chemical composition of lithium- and manganese-rich transition metal oxides used as cathode materials in lithium-ion batteries can significantly impact their long-term viability as storage solutions for clean energy automotive applications. Their structure has been widely debated: conflicting conclusions drawn from individual studies often considering different compositions have made it challenging to reach a consensus and inform future research. Here, complementary electron microscopy techniques over a wide range of length scales reveal the effect of lithium-to-transition metal-ratio on the surface and bulk structure of these materials. We found that decreasing the lithium-to-transition metal-ratio resulted in a significant change in terms of order and atomic-level local composition in the bulk of these cathode materials. However, throughout the composition range studied, the materials consisted solely of a monoclinic phase, with lower lithium content materials showing more chemical ordering defects. In contrast, the spinel-structured surface present on specific crystallographic facets exhibited no noticeable structural change when varying the ratio of lithium to transition metal. The structural observations from this study warrant a reexamination of commonly assumed models linking poor electrochemical performance with bulk and surface structure.

Emergent phenomena at complex oxide interfaces could provide the basis for a wide variety of next-generation devices, including photovoltaics and spintronics. To date, detailed characterization and computational modeling of interfacial defects, cation intermixing, and film stoichiometry have helped to explain many of the novel behaviors observed at a single heterojunction. Unfortunately, many of the techniques employed to characterize a single heterojunction are less effective for a superlattice made up of a repeating series of interfaces that induce collective interfacial phenomena throughout a film. These repeating interfaces present an untapped opportunity to introduce an additional degree of complexity, such as confined electric fields, that cannot be realized in a single heterojunction. In this work, we explore the properties of SrTiO3–LaCrO3 superlattices to understand the role of defects, including variations in cation stoichiometry of individual layers of the superlattice, intermixing across inter...

Donor-doped SrTiO3 ceramics are very promising n-type oxide thermoelectrics. We show that significant improvements in the thermoelectric power factor can be achieved by control of the nanostructure and microstructure. Using additions of B2O3 and ZrO2, high density, high quality Sr0.9Nd0.1TiO3 ceramics were synthesised by the mixed oxide route; samples were heat treated in a single step under reducing atmosphere at 1673 K. Synchrotron and electron diffraction studies revealed an I4/mcm tetragonal symmetry for all specimens. Microstructure development depended on the ZrO2 content; low level additions of ZrO2 (up to 0.3 wt%) led to a uniform grain size with transformation-induced sub-grain boundaries. HRTEM studies showed a high density of dislocations within the grains; the dislocations comprised (100) and (110) edge dislocations with Burger vectors of d(100) and d(110) respectively. Zr doping promoted atomic level homogenization and a uniform distribution of Nd and Sr in the lattice, inducing greatly enhanced carrier mobility. Transport property measurements showed a significant increase in the power factor, mainly resulting from the enhanced electrical conductivity while the Seebeck coefficients were unchanged. In optimised samples a power factor of 2.0 × 10−3 W m−1 K−2 was obtained at 500 K. This is an ∼30% improvement compared to the highest values reported for SrTiO3-based ceramics. The highest ZT value for Sr0.9Nd0.1TiO3 was 0.37 at 1015 K. This paper demonstrates the critical importance of controlling the structure at the atomic level and the effectiveness of minor dopants in enhancing the thermoelectric response.

The depth-resolved chemical structure and magnetic moment of $ \newcommand{\CFAS}{{\rm Co}_{2}{\rm FeAl}_{0.5}{\rm Si}_{0.5}} \CFAS$ , thin films grown on Si(1 1 1) have been determined using x-ray and polarized neutron reflectometry. Bulk-like magnetization is retained across the majority of the film, but reduced moments are observed within 45$~\mathring{\rm A}$ of the surface and in a 25$~\mathring{\rm A}$ substrate-interface region. The reduced moment is related to compositional changes due to oxidation and diffusion, which are further quantified by elemental profiling using electron microscopy with electron energy loss spectroscopy. The accuracy of structural and magnetic depth-profiles obtained from simultaneous modeling is discussed using different approaches with different degree of constraints on the parameters. Our approach illustrates the challenges in fitting reflectometry data from these multi-component quaternary Heusler alloy thin films.

The high-strength weldable 7xxxseries of aluminium alloys are of great importance to the aeronautics industry. Only recently, the complex structures of the AlZnMg hardening precipitates have been solved by HAADFSTEM imaging and first-principles calculations. However, perfect models of precipitate structures are often insufficient as several elements may be mixed into precipitate compositions. We have investigated this effect by STEMEELS spectrum imaging with an aberration-corrected microscope. In a 7449 alloy, Cu and Al were found to replace atoms at certain sites in both metastable and equilibrium ZnMg precipitates.

Magnetoelectric oxide heterostructures are proposed active layers for spintronic memory and logic devices, where information is conveyed through spin transport in the solid state. Incomplete theories of the coupling between local strain, charge, and magnetic order have limited their deployment into new information and communication technologies. In this study, we report direct, local measurements of strain- and charge-mediated magnetization changes in the La0.7Sr0.3MnO3/PbZr0.2Ti0.8O3 system using spatially resolved characterization techniques in both real and reciprocal space. Polarized neutron reflectometry reveals a graded magnetization that results from both local structural distortions and interfacial screening of bound surface charge from the adjacent ferroelectric. Density functional theory calculations support the experimental observation that strain locally suppresses the magnetization through a change in the Mn-eg orbital polarization. We suggest that this local coupling and magnetization suppression may be tuned by controlling the manganite and ferroelectric layer thicknesses, with direct implications for device applications.

Selecting the electrical properties of nanomaterials is essential if their potential as manufacturable devices is to be reached. Here, we show that the addition or removal of native semiconductor material at the edge of a nanocontact can be used to determine the electrical transport properties of metal–nanowire interfaces. While the transport properties of as-grown Au nanocatalyst contacts to semiconductor nanowires are well-studied, there are few techniques that have been explored to modify the electrical behavior. In this work, we use an iterative analytical process that directly correlates multiprobe transport measurements with subsequent aberration-corrected scanning transmission electron microscopy to study the effects of chemical processes that create structural changes at the contact interface edge. A strong metal–support interaction that encapsulates the Au nanocontacts over time, adding ZnO material to the edge region, gives rise to ohmic transport behavior due to the enhanced quantum-mechanical tunneling path. Removal of the extraneous material at the Au–nanowire interface eliminates the edge-tunneling path, producing a range of transport behavior that is dependent on the final interface quality. These results demonstrate chemically driven processes that can be factored into nanowire-device design to select the final properties.

Epitaxial interfaces and superlattices comprised of polar and non-polar perovskite oxides have generated considerable interest because they possess a range of desirable properties for functional devices. In this work, emergent polarization in superlattices of SrTiO$_3$ (STO) and LaCrO$_3$ (LCO) is demonstrated. By controlling the interfaces between polar LCO and non-polar STO, polarization is induced throughout the STO layers of the superlattice. Using x-ray absorption near-edge spectroscopy and aberration-corrected scanning transmission electron microscopy displacements of the Ti cations off-center within TiO6 octahedra along the superlattice growth direction are measured. This distortion gives rise to built-in potential gradients within the STO and LCO layers, as measured by in situ x-ray photoelectron spectroscopy. Density functional theory models explain the mechanisms underlying this behavior, revealing the existence of both an intrinsic polar distortion and a built-in electric field, which are due to alternately positively and negatively charged interfaces in the superlattice. This study paves the way for controllable polarization for carrier separation in multilayer materials and highlights the crucial role that interface structure plays in governing such behavior., 19 pages, 3 figures, supplement: 13 pages, 7 figures, Advanced Materials Interfaces, Early View, 2016

Thin-film oxide heterostructures show great potential for use in spintronic memories, where electronic charge and spin are coupled to transport information. Here we use a La0.7Sr0.3MnO3 (LSMO)/PbZr0.2Ti0.8O3 (PZT) model system to explore how local variations in electronic and magnetic phases mediate this coupling. We present direct, local measurements of valence, ferroelectric polarization and magnetization, from which we map the phases at the LSMO/PZT interface. We combine these experimental results with electronic structure calculations to elucidate the microscopic interactions governing the interfacial response of this system. We observe a magnetic asymmetry at the LSMO/PZT interface that depends on the local PZT polarization and gives rise to gradients in local magnetic moments; this is associated with a metal-insulator transition at the interface, which results in significantly different charge-transfer screening lengths. This study establishes a framework to understand the fundamental asymmetries of magnetoelectric coupling in oxide heterostructures.

The passage of an electric current through graphite or few-layer graphene can result in a striking structural transformation, but there is disagreement about the precise nature of this process. Some workers have interpreted the phenomenon in terms of the sublimation and edge reconstruction of essentially flat graphitic structures. An alternative explanation is that the transformation actually involves a change from a flat to a three-dimensional structure. Here we describe detailed studies of carbon produced by the passage of a current through graphite which provide strong evidence that the transformed carbon is indeed three-dimensional. The evidence comes primarily from images obtained in the scanning transmission electron microscope using the technique of high-angle annular dark-field imaging, and from a detailed analysis of electron energy loss spectra. We discuss the possible mechanism of the transformation, and consider potential applications of 'three-dimensional bilayer graphene'.

Aberration-corrected scanning transmission electron microscopy combined with electron energy loss spectroscopy has been used to determine the distribution of Cu and Ag atomic columns of precipitates in an Al–Mg–Si–Cu–Ag alloy. Cu columns were commonly part of C and Q′ phases, with the atomic columns having large projected separations. Columns containing Ag were more tightly spaced, in areas lacking repeating unit cells and at incoherent precipitate–host lattice interfaces. Cu-rich and Ag-rich areas were not found to intermix. This is a submitted manuscript of an article published by Elsevier Ltd in Scripta Materialia, 11 November 2013.

Knowing and controlling the resistivity of an individual nanowire (NW) is crucial for the production of new sensors and devices. For ZnO NWs this is poorly understood; a 10(8) variation in resistivity has previously been reported, making the production of reproducible devices almost impossible. Here, we provide accurate resistivity measurements of individual NWs, using a four-probe scanning tunnelling microscope (STM), revealing a dependence on the NW dimensions. To correctly interpret this behaviour, an atomic level transmission electron microscopy technique was employed to study the structural properties of the NWs in relation to three growth techniques: hydrothermal, catalytic and non-catalytic vapour phase. All NWs were found to be defect free and structurally equivalent; those grown with a metallic catalyst were free from Au contamination. The resistivity measurements showed a distinct increase with decreasing NW diameter, independent of growth technique. The increasing resistivity at small NW diameters was attributed to the dominance of surface states removing electrons from the bulk. However, a fundamental variance in resistivity (10(2)) was observed and attributed to changes in occupied surface state density, an effect which is not seen with other NW materials such as Si. This is examined by a model to predict the effect of surface state occupancy on the measured resistivity and is confirmed with measurements after passivating the ZnO surface. Our results provide an understanding of the primary influence of the reactive nature of the surface and its dramatic effect on the electrical properties of ZnO NWs.