Search

The physics of phase transitions in two-dimensional (2D) systems underpins research in diverse fields including statistical mechanics, nanomagnetism, and soft condensed matter. However, many aspects of 2D phase transitions are still not well understood, including the effects of interparticle potential, polydispersity, and particle shape. Magnetic skyrmions are chiral spin-structure quasi-particles that form two-dimensional lattices. Here, we show, by real-space imaging using

The effect of confinement on electron and ion transport in oxide films is of interest both fundamentally and technologically for the design of next-generation electronic devices. In metal oxides with mobile ions and vacancies, it is the interplay of the different modes of charge transport and the corresponding current-voltage signatures that is of interest. We developed a patterned structure in titania films, with feature sizes of 11-20 nm, that allow us to explore confined transport. We describe how confinement changes the competing charge transport mechanisms, the patterned antidot array leads to displacement fields and confines the charge density that results in modified and emergent electron transport with an increase in conductivity. This emergent behavior can be described by considering electron interference effects. Characterization of the charge transport with electron holography and impedance spectroscopy, and through comparison with modeling, show that nanoscale confinement is a way to control quantum interference.

FeNi-based metal amorphous nanocomposite alloys are emerging soft magnetic materials with promise for high-speed motor applications. Here we demonstrate a technique to optimize magnetic properties in toroidal cores wound from strain annealed (Fe70Ni30)80Nb4Si2B14 amorphous metal ribbon (AMR). In-line strain annealing (SA) of the AMR yields a strip permeability that monotonically decreases with increasing SA tensions. After winding into toroidal cores, dramatic changes in magnetic properties are observed and determined to be of magnetostrictive origin. A procedure to re-anneal wound toroidal cores to reduce hysteresis and reverse magnetostrictive effects is developed inclusive of casting curvature effects. We investigate re-annealing temperatures between 300 – 470 °C for cores produced from each SA condition. Magnetic core loss, WL, coercivity, Hc, squareness ratio, Kr, and permeability, µr are measured as a function of (stress relief) re-annealing temperature to optimally achieve W1T,400 Hz = 0.51 W/kg, Hc = 2.42 A/m, Kr = 0.22, and µr = 35,300.

Three-dimensional fabrication of nanostructures opens unique possibilities to not only understand the fundamental effects of shape and of the interactions between the nanostructures, but also for t...

Here, we consider theoretical description and fabrication of thin wires, which are arranged along space curves. Geometry of these nanoarchitectures is characterized by two functions: curvature and torsion, which determine the modification of magnetic responses. The torsion being the key distinguishing parameter from flat curvilinear wires (discussed in Chapter 1) is in the focus of this chapter. The presented analytical approach to address thin wires of circular cross-section (wires) and rectangular cross-section (thin ribbons) deals with the geometry-induced effects stemming from the symmetric and antisymmetric exchange, as well as symmetries of spin-orbit and spin-transfer torques. Using helix- and helicoid-based samples as a case study, we discuss fundamental features in magnetic textures of geometries with twists in three-dimensional space and compare properties of ferromagnetic samples with antiferromagnetic spin chains. The experimental techniques to develop and characterize ferromagnetic nanowires of arbitrary shape at the nanoscale are described.

Two-dimensional magnetic van der Waals (vdW) materials can show a variety of topological nontrivial spin textures, such as Bloch- or N\'eel-type stripe, skyrmion or bubble domains under certain external stimuli. It is critical to understand the magnetic domain behavior in vdW materials in order to control their size, and density in response to external stimuli such as electric and magnetic fields. Here we examine the magnetic field dependence of topologically non-trivial magnetization spin textures in vdW Fe$_3$GeTe$_2$. N\'eel-type stripe domains and skyrmions are formed depending on the magnetic field-cooling protocol used during in-situ Lorentz transmission electron microscopy (LTEM) experiments. Use of quantitative reconstruction of magnetic induction maps, and micromagnetic simulations, allow for understanding the LTEM results of N\'eel-type stripe domains as well as skyrmions. In addition, the deformation of skyrmion contrast is observed as a result of the introduction of an in-plane magnetic field. We demonstrate the stability of the stripe domains and skyrmions in response to externally applied magnetic field due to energy barrier for domain wall annihilation. Our results establish an understanding of the energy landscape that governs the behavior of the topologically non-trivial spin textures in vdW materials which can be harnessed for spintronic applications., Comment: 16 pages, 5 figures

The future of next-generation rechargeable batteries, such as lithium metal, lithium–sulfur, and lithium–oxygen batteries, hinges on the utilization of metallic lithium as the anode. However, the p...

Lithium metal is considered one of the most promising anode materials for realizing high volumetric and gravimetric energy density, owing to the high specific capacity (∼3860 mAh g−1) and the low electrochemical potential of lithium (−3.04 V vs. the standard hydrogen electrode). However, undesirable dendritic lithium growth and corresponding instability of the solid electrolyte interphase prevent safe and long-term use of lithium metal anodes. This paper presents a simple electrolyte approach to enhance the performance of lithium metal batteries by tuning the dielectric constant of the liquid electrolyte. Electrolyte formulations are designed by changing the concentration of ethylene carbonate to have various dielectric constants. This study confirms that high ethylene carbonate content in a liquid electrolyte enhances the cycling performance of lithium metal batteries because the electric field intensity applied to the electrolyte is reduced in relation to the polarization of the electrolyte and thus allows smooth lithium plating and formation of a stable solid electrolyte interphase. We believe that this approach provides an important concept for electrolyte system design suitable to lithium metal batteries.

Two micro-patterns of different sizes (50 and 80 μm) are designed to have equivalent capacities of 1.06 and 2.44 mAh cm−2 by building a computational battery model. After preparing two stamps each possessing a micro-pattern design, the corresponding pattern is properly imprinted on the surface of 100 μm lithium metal, which is confirmed by scanning electron microscopy. When both micro-patterned lithium metals are electrochemically reduced and oxidized up to 1 mAh cm−2 in Li/Li symmetric cells at 1 or 2 mA cm−2, the 80 μm-patterned lithium shows a more stabilized lower overpotential during long-term cycling than the 50 μm-patterned and bare lithium, probably due to the lithium anchoring effect and a larger empty volume in the patterns. Additionally, an overflow of lithium deposits is easily observed in the 50 μm-patterned lithium metal, while the 80 μm-patterned lithium metal holds most of the lithium deposits within the patterns. When both micro-patterned lithium metals are assembled to full cells with a LiNi0·6Co0·2Mn0·2O2 cathode of 2 mAh cm−2, the 80 μm-patterned lithium metal shows much better electrochemical performances with stable plating/stripping behavior within the patterns.

Lorentz transmission electron microscopy (LTEM) is frequently used to image magnetic induction maps of topological magnetic spin structures. These induction maps are visually intuitive, but can be misinterpreted for materials in which the magnetization differs greatly from the integrated induction, leading to ambiguous determination of spin structures. The authors present PyLorentz, their open-source software for simulating LTEM images from three-dimensional micromagnetic simulations. By applying the technique to N\'eel skyrmions, they demonstrate that combining simulated and experimental LTEM images gives a more complete picture of complex spin structures.

Vector field electron tomography (VFET) is extensively used for three-dimensional (3-D) imaging of magnetic materials at nanometer resolutions. The conventional approach is to reconstruct and visualize the magnetic vector potential or the magnetic field associated with the sample. There is a lack of algorithms capable of reconstructing the 3-D distribution of magnetization from VFET data. Unlike magnetic vector potential and magnetic field, magnetization is a fundamental physical property of the sample that does not extend beyond the dimensions of the sample. We present a model-based iterative reconstruction algorithm (MBIR) that reconstructs the magnetization by minimizing a cost function consisting of a forward model term and a prior model term. The forward model uses the physics of imaging to model the VFET data as a function of the magnetization, and the prior model enforces sparsity in the magnetization reconstruction. We then formulate an optimization algorithm based on the theory of alternate direction method of multipliers to minimize the resulting MBIR cost function. Using simulated and real data, we show that our algorithm accurately reconstructs both the magnetization and the magnetic vector potential.

One of the challenges in developing Lithium anodes for Lithium ion batteries (LIB) is controlling the formation of Li dendrites during cycling of the battery. Nanostructuring and nanopatterning of electrodes shows a promising way to suppress the growth of Li dendrites. However, in order to control this behavior, a fundamental understanding of the effect of nanopatterning on the electro-mechanical properties of Li metal is necessary. In this paper, we have investigated the mechanical and wear properties of Li metal using Atomic Force Microscopy (AFM) in an airtight cell. By using different load regimes, we determined the mechanical properties of Li metal. We show that as a result of nanopatterning, Li metal surface underwent work hardening due to residual compressive stress. The presence of such stresses can help to improve cycle lifetime of LIBs with Li anodes and obtain very high energy densities. Keywords: Nanopatterning, mechanical properties, Li anode, Lithium ion batteries

Analytical electron microscopy and spectroscopy of biological specimens, polymers, and other beam sensitive materials has been a challenging area due to irradiation damage. There is a pressing need to develop novel imaging and spectroscopic imaging methods that will minimize such sample damage as well as reduce the data acquisition time. The latter is useful for high-throughput analysis of materials structure and chemistry. In this work, we present a novel machine learning based method for dynamic sparse sampling of EDS data using a scanning electron microscope. Our method, based on the supervised learning approach for dynamic sampling algorithm and neural networks based classification of EDS data, allows a dramatic reduction in the total sampling of up to 90%, while maintaining the fidelity of the reconstructed elemental maps and spectroscopic data. We believe this approach will enable imaging and elemental mapping of materials that would otherwise be inaccessible to these analysis techniques.

In order to increase the storage density of hard disk drives, a detailed understanding of the magnetic structure of the granular magnetic layer is essential. Here, we demonstrate an experimental procedure of imaging recorded bits on heat-assisted magnetic recording (HAMR) media in cross section using Lorentz transmission electron microscopy (TEM). With magnetic force microscopy and focused ion beam (FIB), we successfully targeted a single track to prepare cross-sectional TEM specimens. Then, we characterized the magnetic structure of bits with their precise location and orientation using Fresnel mode of Lorentz TEM. This method can promote understanding of the correlation between bits and their material structure in HAMR media to design better the magnetic layer.

We have studied the ferroelectric domains in (001) BiFeO3 (BFO) films patterned into mesas with various aspect ratios, using angle-resolved piezoresponse force microscope (AR-PFM), which can image the in-plane polarization component with an angular resolution of 30°. We observed not only stable polarization variants, but also meta-stable polarization variants, which can reduce the charge accumulated at domain boundaries. We considered the number of neighboring domains that are in contact, in order to analyze the complexity of the ferroelectric domain structure. Comparison of the ferroelectric domains from the patterned and unpatterned regions showed that the elastic relaxation induced by removal of the film surrounding the mesas led to a reduction of the average number of neighboring domains, indicative of a decrease in domain complexity. We also found that the rectangular BFO patterns with high aspect ratio had a simpler domain configuration and enhanced piezoelectric characteristics than square-shaped mesas. Manipulation of the ferroelectric domains by controlling the aspect ratio of the patterned BFO thin film mesas can be useful for nanoelectronic applications.

A number of grain boundary phenomena in ionic materials, in particular, anomalous (either depressed or enhanced) charge transport, have been attributed to space charge effects. Developing effective strategies to manipulate transport behaviour requires deep knowledge of the origins of the interfacial charge, as well as its variability within a polycrystalline sample with millions of unique grain boundaries. Electron holography is a powerful technique uniquely suited for studying the electric potential profile at individual grain boundaries, whereas atom-probe tomography provides access to the chemical identify of essentially every atom at individual grain boundaries. Using these two techniques, we show here that the space charge potential at grain boundaries in lightly doped, high-purity ceria can vary by almost an order of magnitude. We further find that trace impurities (

Artificial spin ices (ASIs) are nanoscale geometrically engineered arrays of magnetic bars or islands that display magnetic frustration and provide a fertile system for modeling and testing many complex statistical mechanics theories and emergent phenomena. Aperiodic ASIs display spatially varying magnetic frustration as a result of the aperiodicity. We have explored the magnetization reversal of quasicrystalline ASIs (QC-ASIs) patterned on P2 and P3 Penrose tilings, using a statistical graph-theory approach that enables quantitative comparison between the two tilings. Our approach offers insight into the QC-ASIs. We show that the P2 tiling leads to enhanced topological frustration compared to the P3 tiling, and we elucidate the emergence of local antiferromagnetic ordering as well as disordered states in these ferromagnetic aperiodic lattices. Our method enables quantitative exploration of frustration behavior on any periodic or aperiodic lattice, thereby opening pathways to study collective behavior in various topologically frustrated systems.

Magnetic skyrmions are topological spin textures that have been observed in bulk magnets and magnetic multilayers. For bulk magnetic materials, their noncollinear spin profiles have often been studied by using Lorentz transmission electron microscopy (TEM). We experimentally utilized Lorentz TEM imaging to study an inversion asymmetric ${[\mathrm{Pt}(1.5\phantom{\rule{0.16em}{0ex}}\mathrm{nm})/\mathrm{Co}(1\phantom{\rule{0.16em}{0ex}}\mathrm{nm})/\mathrm{W}(1\phantom{\rule{0.16em}{0ex}}\mathrm{nm})]}_{8}$ heterostructure that exhibits N\'eel-type skyrmions at zero field. By tracking the evolution of skyrmion diameters as a function of magnetic fields, we determined the strength of the interfacial Dzyaloshinskii-Moriya interaction (DMI). Our results suggest that in situ Lorentz TEM imaging combined with simulations can provide valuable quantitative information about the interfacial DMI strengths, which can be helpful for optimizing skyrmion materials. Furthermore, we show that in theory, Lorentz TEM can identify the spin chirality of N\'eel-type skyrmions, although an experimental verification is challenging due to the relatively low signal-to-noise ratio.

Geometric curvature in magnetic systems can induce several unique magnetic interactions, the most notable of which are the curvature induced magnetic anisotropy and the curvature introduced Dzyaloshinski–Moria (DM) like interaction. Of the two, the DM-like interaction is particularly interesting as it provides a unique way to control domain wall motion, which is particularly relevant to the field of spintronics. In this work, we study the effect of geometric curvature on magnetization reversal in Permalloy strips patterned into Archimedean spirals with varying widths. We simulated the magnetization reversal of Permalloy strips for several widths ranging from microscale to nanoscale to determine a lengthscale at which the curvature effects are strong. Simulations showed that in the microscale spirals, magnetization reversal primarily occurs through the appearance of magnetization ripple in which domains with reversed magnetization nucleate. On the other hand, the nanoscale spirals showed that reversal primarily proceeded through the motion of domain walls into the arms of the spiral. Our experimental in situ Lorentz transmission electron microscopy data of the microscale spirals, however, showed that magnetization reversal occurred with both mechanisms. At the nanoscale, the effect of local variation of curvature leads to hysteresis loops with stepped behavior. This behavior is characteristic of the curvature induced DM-like interaction affecting domain wall motion in the arms of the nanoscale spirals.

The use of lithium metal in secondary batteries has been impeded by its tendency to form dendrites: branching conductive structures of metal that can lead to capacity loss and, ultimately, internal shorts in the battery. Patterned electrodes, in addition to artificially increasing the current density of cells by increasing the surface area available for reaction, also generate a nonuniform electric field in the vicinity of the electrode surface. This nonuniform electric field, though rapidly screened by the electrolyte, can promote inhomogeneous deposition and Solid Electrolyte Interphase formation. As the consequence of these effects is not theoretically apparent since Solid Electrolyte Interphase volume and conductivity changes can, in principle, offset variations in local current density, we have performed experiments to examine the deposition of Li on nonuniform electrode surfaces using Atomic Force Microscopy. We measure the local variations in topography, SEI thickness, and composition, and discuss their implications for the formation of dendrites in Li metal.

The electrical properties of interfaces in semiconductors and ionic conductors are immensely important in a wide range of applications. Electron holography is ideally suited for the direct measurement of the electrostatic potential of such interfaces. A key challenge with this approach is the contribution of the leakage field from the sample to the observed electron phase shift. This leakage field cannot be a priori independently determined and can cause an overestimation of the phase shift. In this work, we use finite element simulations to compute the three-dimensional electrostatic potential in the vicinity of an interface associated with a given interfacial charge density distribution. We then evaluate the predicted phase shift and demonstrate that the leakage field strongly affects the recovery of the projected interface potential. From the difference between the true potential and uncorrected, recovered potential, we propose a method to correct for this effect. We then demonstrate the application of this methodology to the analysis of experimental off-axis electron holography data acquired from the grain boundaries in lightly doped ceria.

Lorentz transmission electron microscopy (LTEM) has evolved from a qualitative magnetic domain observation technique to a quantitative technique for the determination of the magnetization state of a sample. In this review article, we describe recent developments in techniques and imaging modes, including the use of spherical aberration correction to improve the spatial resolution of LTEM into the single nanometer range, and novel in situ observation modes. We review recent advances in the modeling of the wave optical magnetic phase shift as well as in the area of phase reconstruction by means of the Transport of Intensity Equation (TIE) approach, and discuss vector field electron tomography, which has emerged as a powerful tool for the 3D reconstruction of magnetization configurations. We conclude this review with a brief overview of recent LTEM applications.

Artificial spin ices (ASIs) consisting of arrays of magnetic bars are key systems in the study of geometric frustration in magnetic systems. Of particular interest are quasicrystal (QC) ASIs, in which the lack of translational symmetry and the varying coordination number of interacting bars allow for topologically enhanced frustrated magnetization to occur. We have directly observed the formation of magnetic vortexes within the vertices of a QC-ASI as a metastable transient state, during the magnetization reversal process. We observed that the vortexes primarily form in a specific subset of the vertex motif types. Micromagnetic simulations show that although these magnetic vortexes result in an increase in the local energy of the vertex before the magnetization of the bars reverses to align with the applied magnetic field, the overall energy increase is lower than the higher energy motif configurations that would result from reversal of the magnetization in the connecting bar.

The development of magnetic nanostructures for applications in spintronics requires methods capable of visualizing their magnetization. Soft X-ray magnetic imaging combined with circular magnetic dichroism allows nanostructures up to 100–300 nm in thickness to be probed with resolutions of 20–40 nm. Here a new iterative tomographic reconstruction method to extract the three-dimensional magnetization configuration from tomographic projections is presented. The vector field is reconstructed by using a modified algebraic reconstruction approach based on solving a set of linear equations in an iterative manner. The application of this method is illustrated with two examples (magnetic nano-disc and micro-square heterostructure) along with comparison of error in reconstructions, and convergence of the algorithm., The following funding is acknowledged: Spanish MINECO (grant No. FIS2013-45469; grant No. FIS2016-76058 (AEI/FEDER, EU); contract No. FIS2016-76058 (AEI/FEDER, EU) to AHR); FICYT-Asturias (grant No. FC-GRUPIN14-040); US Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory (contract No. DE-AC02-06CH11357 to DG); US Department of Energy, Office of Science, Office of Basic Energy Sciences, Materials Sciences and Engineering Division (contract to CP). AHR acknowledges support from European Union’s Horizon 2020 research and innovation program under the Marie Skłodowska-Curie Action (reference H2020-MSCA-IF-2016-746958).

Lorentz Transmission Electron Microscopy (TEM) observations of magnetic nanoparticles contain information on the magnetic and electrostatic potentials. Vector Field Electron Tomography (VFET) can be used to reconstruct electromagnetic potentials of the nanoparticles from their corresponding LTEM images. The VFET approach is based on the conventional filtered back projection approach to tomographic reconstructions and the availability of an incomplete set of measurements due to experimental limitations means that the reconstructed vector fields exhibit significant artifacts. In this paper, we outline a model-based iterative reconstruction (MBIR) algorithm to reconstruct the magnetic vector potential of magnetic nanoparticles. We combine a forward model for image formation in TEM experiments with a prior model to formulate the tomographic problem as a maximum a-posteriori probability estimation problem (MAP). The MAP cost function is minimized iteratively to determine the vector potential. A comparative reconstruction study of simulated as well as experimental data sets show that the MBIR approach yields quantifiably better reconstructions than the VFET approach., 28 pages, 14 figures, submitted to Ultramicroscopy

Here, we report the observation of ferroelectric and ferroelastic nanodomains in (110)-oriented BiFeO3 (BFO) thin films epitaxially grown on low symmetric (100) NdGaO3 (NGO) substrate. We observed long range ordering of ferroelectric 109° stripe nanodomains separated by periodic vertical domain walls in as-grown 130 nm thick BFO films. The effect of La0.67Sr0.33CoO3 (LSCO) conducting interlayer on domain configurations in BFO/NGO film was also observed with relatively short range-ordering of stripe domains due to the modified electrostatic boundary conditions in BFO/LSCO/NGO film. Additional studies on B-site doping of Nb ions in BFO films showed change in the domain structures due to doping induced change in lattice anisotropy while maintaining the stripe domain morphology with 109° domain wall. This long-range array of ferroelectric and ferroelastic domains can be useful for optoelectronic devices and ferroelastic templates for strain coupled artificial magnetoelectric heterostructures.

A convolutional neural network (CNN) classifier is trained using simulated energy-dispersive spectroscopy data. The CNN incorporated within a dynamic sampling method is to reduce radiation exposure and data acquisition time for elemental mapping.

We previously demonstrated that TiOx/Al2O3 nanolaminates (TAO NL) exhibit abnormally high-dielectric constant k (800–1000), due to Maxwell–Wagner polarization, via charge accumulation at insulating Al2O3/semiconducting TiOx interfaces. Here, we report TAO NL dielectric properties related to TiOx phase change in TiOx (0.9 nm)/Al2O3 (0.1 nm) NL. High-resolution transmission electron microscopy shows amorphous TiOx phase change to crystalline anatase TiO2 due to free-energy minimization. The phase change induce reduction in leakage current and dielectric loss (J = 10−2 to 10−4 A/cm2, tan δ = 10 to 10−1), still with k ∼ 600 up to MHz, compared to amorphous TAO NLs.

We introduce a new approach for the separation of the electrostatic and magnetic components of the electron wave phase shift, based on the transport-of-intensity equation (TIE) formalism. We derive two separate TIE-like equations, one for each of the phase shift components. We use experimental results on FeCoB and Permalloy patterned islands to illustrate how the magnetic and electrostatic longitudinal derivatives can be computed. The main advantage of this new approach is the fact that the differences in the power spectra of the two phase components (electrostatic phase shifts often have significant power in the higher frequencies) can be accommodated by the selection of two different Tikhonov regularization parameters for the two phase reconstructions. The extra computational demands of the method are more than compensated by the improved phase reconstruction results.

The interaction between X-rays and matter is an intriguing topic for both fundamental science and possible applications. In particular, synchrotron-based brilliant X-ray beams have been used as a powerful diagnostic tool to unveil nanoscale phenomena in functional materials. However, it has not been widely investigated how functional materials respond to the brilliant X-rays. Here, we report the X-ray-induced reversible resistance change in 40-nm-thick TiO2 films sandwiched by Pt top and bottom electrodes, and propose the physical mechanism behind the emergent phenomenon. Our findings indicate that there exists a photovoltaic-like effect, which modulates the resistance reversibly by a few orders of magnitude, depending on the intensity of impinging X-rays. We found that this effect, combined with the X-ray irradiation induced phase transition confirmed by transmission electron microscopy, triggers a nonvolatile reversible resistance change. Understanding X-ray-controlled reversible resistance changes can provide possibilities to control initial resistance states of functional materials, which could be useful for future information and energy storage devices.