Physical Delithiation of Epitaxial LiCoO2 Battery Cathodes as a Platform for Surface Electronic Structure Investigation.

We report a novel delithiation process for epitaxial thin films of LiCoO2(001) cathodes using only physical methods, based on ion sputtering and annealing cycles. Preferential Li sputtering followed by annealing produces a surface layer with a Li molar fraction in the range 0.5 < x < 1, characterized by good crystalline quality. This delithiation procedure allows the unambiguous identification of the effects of Li extraction without chemical byproducts and experimental complications caused by electrolyte interaction with the LiCoO2 surface. An analysis by X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS) provides a detailed description of the delithiation process and the role of O and Co atoms in charge compensation. We observe the simultaneous formation of Co4+ ions and of holes localized near O atoms upon Li removal, while the surface shows a (2 × 1) reconstruction. The delithiation method described here can be applied to other crystalline battery elements and provide information on their properties that is otherwise difficult to obtain.

Stacking influence on the in-plane magnetic anisotropy in a 2D magnetic system.

The magnetization patterns on three atomic layers thick islands of Co on Ru(0001) are studied by spin-polarized low-energy electron microscopy (SPLEEM). In-plane magnetized micrometer wide triangular Co islands are grown on Ru(0001). They present two different orientations correlated with two different stacking sequences which differ only in the last layer position. The stacking sequence determines the type of magnetization pattern observed: the hcp islands present very wide domain walls, while the fcc islands present domains separated by much narrower domain walls. The former is an extremely low in-plane anisotropy system. We estimate the in-plane magnetic anisotropy of the fcc regions to be 1.96 × 104 J m-3 and of the hcp ones to be 2.5 × 102 J m-3.

Imaging Phase Segregation in Nanoscale LixCoO2 Single Particles.

LixCoO2 (LCO) is a common battery cathode material that has recently emerged as a promising material for other applications including electrocatalysis and as electrochemical random access memory (ECRAM). During charge-discharge cycling LCO exhibits phase transformations that are significantly complicated by electron correlation. While the bulk phase diagram for an ensemble of battery particles has been studied extensively, it remains unclear how these phases scale to nanometer dimensions and the effects of strain and diffusional anisotropy at the single-particle scale. Understanding these effects is critical to modeling battery performance and for predicting the scalability and performance of electrocatalysts and ECRAM. Here we investigate isolated, epitaxial LiCoO2 islands grown by pulsed laser deposition. After electrochemical cycling of the islands, conductive atomic force microscopy (c-AFM) is used to image the spatial distribution of conductive and insulating phases. Above 20 nm island thicknesses, we observe a kinetically arrested state in which the phase boundary is perpendicular to the Li-planes; we propose a model and present image analysis results that show smaller LCO islands have a higher conductive fraction than larger area islands, and the overall conductive fraction is consistent with the lithiation state. Thinner islands (14 nm), with a larger surface to volume ratio, are found to exhibit a striping pattern, which suggests surface energy can dominate below a critical dimension. When increasing force is applied through the AFM tip to strain the LCO islands, significant shifts in current flow are observed, and underlying mechanisms for this behavior are discussed. The c-AFM images are compared with photoemission electron microscopy images, which are used to acquire statistics across hundreds of particles. The results indicate that strain and morphology become more critical to electrochemical performance as particles approach nanometer dimensions.

Helical surface magnetization in nanowires: the role of chirality.

Nanomagnetism is nowadays expanding into three dimensions, triggered by the discovery of new magnetic phenomena and their potential use in applications. This shift towards 3D structures should be accompanied by strategies and methodologies to map the tridimensional spin textures associated. We present here a combination of dichroic X-ray transmission microscopy at different angles and micromagnetic simulations allowing to determine the magnetic configuration of cylindrical nanowires. We have applied it to permalloy nanowires with equispaced chemical barriers that can act as pinning sites for domain walls. The magnetization at the core is longitudinal and generates at the surface of the wire helical magnetization. Different types of domain walls are found at the pinning sites, which respond differently to applied fields depending on the relative chirality of the adjacent domains.

Large Dzyaloshinskii-Moriya interaction induced by chemisorbed oxygen on a ferromagnet surface.

The Dzyaloshinskii-Moriya interaction (DMI) is an antisymmetric exchange interaction that stabilizes chiral spin textures. It is induced by inversion symmetry breaking in noncentrosymmetric lattices or at interfaces. Recently, interfacial DMI has been found in magnetic layers adjacent to transition metals due to the spin-orbit coupling and at interfaces with graphene due to the Rashba effect. We report direct observation of strong DMI induced by chemisorption of oxygen on a ferromagnetic layer at room temperature. The sign of this DMI and its unexpectedly large magnitude-despite the low atomic number of oxygen-are derived by examining the oxygen coverage-dependent evolution of magnetic chirality. We find that DMI at the oxygen/ferromagnet interface is comparable to those at ferromagnet/transition metal interfaces; it has enabled direct tailoring of skyrmion's winding number at room temperature via oxygen chemisorption. This result extends the understanding of the DMI, opening up opportunities for the chemisorption-related design of spin-orbitronic devices.

Observation of a topologically protected state in a magnetic domain wall stabilized by a ferromagnetic chemical barrier.

The precise control and stabilization of magnetic domain walls is key for the development of the next generation magnetic nano-devices. Among the multitude of magnetic configurations of a magnetic domain wall, topologically protected states are of particular interest due to their intrinsic stability. In this work, using XMCD-PEEM, we have observed a topologically protected magnetic domain wall in a ferromagnetic cylindrical nanowire. Its structure is stabilized by periodic sharp alterations of the chemical composition in the nanowire. The large stability of this topologically protected domain wall contrasts with the mobility of other non-protected and non-chiral states also present in the same nanowire. The micromagnetic simulations show the structure and the conditions required to find the topologically protected state. These results are relevant for the design of future spintronic devices such as domain wall based RF oscillators or magnetic memories.

Memory effect and magnetocrystalline anisotropy impact on the surface magnetic domains of magnetite(001).

The structure of magnetic domains, i.e. regions of uniform magnetization separated by domain walls, depends on the balance of competing interactions present in ferromagnetic (or ferrimagnetic) materials. When these interactions change then domain configurations also change as a result. Magnetite provides a good test bench to study these effects, as its magnetocrystalline anisotropy varies significantly with temperature. Using spin-polarized electron microscopy to map the micromagnetic domain structure in the (001) surface of a macroscopic magnetite crystal (~1 cm size) shows complex domain patterns with characteristic length-scales in the micrometer range and highly temperature dependent domain geometries. Although heating above the Curie temperature erases the domain patterns completely, cooling down reproduces domain patterns not only in terms of general characteristics: instead, complex microscopic domain geometries are reproduced in almost perfect fidelity between heating cycles. A possible explanation of the origin of the high-fidelity reproducibility is suggested to be a combination of the presence of hematite inclusions that lock bulk domains, together with the strong effect of the first order magnetocrystalline anisotropy which competes with the shape anisotropy to give rise to the observed complex patterns.

Geometrically defined spin structures in ultrathin Fe3O4 with bulk like magnetic properties.

We have grown high quality magnetite microcrystals free from antiphase boundaries on Ru(0001) by reactive molecular beam epitaxy, conserving bulk magnetic properties below 20 nm thickness. Magnetization vector maps are obtained by X-ray spectromicroscopy and compared with micromagnetic simulations. The observed domain configurations are dictated purely by shape anisotropy, overcoming the possible influences of (magneto)crystalline anisotropy and defects, thus demonstrating the possibility of designing spin structures in ultrathin, magnetically soft magnetite at will.

Antiferromagnetic FeMn alloys electrodeposited from chloride-based electrolytes.

The capability of synthesizing Fe-based antiferromagnetic metal alloys would fuel the use of electrodeposition in the design of new magnetic devices such as high-aspect-ratio spin valves or new nanostructured hard magnetic composites. Here we report the synthesis of high quality antiferromagnetic FeMn alloys electrodeposited from chloride-based electrolytes. We have found that in order to grow homogeneous FeMn films it is necessary to incorporate a large concentration of NH4Cl as an additive in the electrolyte. The study of the structure and magnetic properties shows that films with composition close to Fe50Mn50 are homogeneous antiferromagnetic alloys. We have established a parameter window for the synthesis of FeMn alloys that show antiferromagnetism at room temperature.

Ge(001) as a template for long-range assembly of π-stacked coronene rows.

The adsorption of coronene molecules (C(24)H(12)) on the Ge(001) surface has been studied by means of scanning tunnelling microscopy (STM). Upon room temperature deposition, the coronene molecules adsorb in an upright geometry forming compact layers patterned in rows for coverages of one monolayer and less, being the only example investigated so far in which a pure aromatic hydrocarbon forms a well-ordered monolayer on a non-passivated semiconductor surface. At half monolayer, the molecular rows consist of long chains of π-stacked molecules and the distance between molecular planes is 8 Å. This configuration is maintained upon cooling the system below the transition temperature of Ge(001) (~220 K), but the molecular layer experiences also a transition from rows perpendicular to rows parallel to the Ge dimer rows. We interpret our observations in terms of a weak bonging between molecules and substrate, which facilitates the formation of large ordered domains of molecules, revealing Ge(001) as an ideal template for the growth of this and other aromatic hydrocarbons.

Valence band circular dichroism in non-magnetic Ag/Ru(0001) at normal emission.

For the non-magnetic system of Ag films on Ru(0001), we have measured the circular dichroism of photoelectrons emitted along the surface normal, the geometry typically used in photoemission electron microscopy. Photoemission spectra were acquired from micrometer-sized regions having uniformly thick Ag films on a single, atomically flat Ru terrace. For a single Ag layer, we find a circular dichroism that exceeds 6% at the d-derived band region around 4.5 eV binding energy. The dichroism decreases as the Ag film thickness increases to three atomic layers. We discuss the origin of the circular dichroism in terms of the symmetry lowering that can occur even in normal emission.

Coexistence of racemic and homochiral two-dimensional lattices formed by a prochiral molecule: dicarboxystilbene on Cu(110).

Dicarboxystilbene, a molecule that becomes chiral in the adsorbed state through the loss of its improper axis of rotation, forms long-range "handed" structures when adsorbed on Cu(110) as revealed by scanning tunnelling microscopy. We show that these structures are created from chiral "adsorption complex" building blocks, giving rise to a complete set of racemic and enantiomerically pure structural assemblies. We interpret the formation of these structures in terms of a balance between hydrogen bond mediated intermolecular interactions and the adsorbate-surface structural relationship and discuss the reasons for temperature-induced conversion from the metastable enantiomerically pure to the racemic structure.