Size effect on excess resistivity induced by hydrogen in ultra-thin vanadium systems.

Through combining a four-point probe and an optical technique, a profound vanadium(v) size effect on the change in excess resistivity during hydrogenation is observed in Fen/V7n (n = 2, 4) superlattices at c ≥ 0.05 H/V. This phenomenon highly emphasizes the effect of interface and H-H interaction on the electrical properties of hydrogen in these systems.

Finite-size effects: hydrogen in Fe/V(001) superlattices.

We investigate the effect of finite size on phase boundaries of hydride formation in ultrathin metallic films, using Fe/V(001) superlattices as a model system. The critical temperature is determined to scale linearly with the inverse thickness of the V layers. The decrease of the ordering temperature with decreasing layer thickness arises from the missing H neighbors at the interfaces, analogous to observed finite-size effects in magnetic layers and nanosized ice crystals.

Nanoscale Clustering in an Additively Manufactured Zr-Based Metallic Glass Evaluated by Atom Probe Tomography.

Composition analysis at the nm-scale, marking the onset of clustering in bulk metallic glasses, can aid the understanding and further optimization of additive manufacturing processes. By atom probe tomography, it is challenging to differentiate nm-scale segregations from random fluctuations. This ambiguity is due to the limited spatial resolution and detection efficiency. Cu and Zr were selected as model systems since the spatial distributions of the isotopes therein constitute ideal solid solutions, as the mixing enthalpy is, by definition, zero. Close agreement is observed between the simulated and measured spatial distributions of the isotopes. Having established the signature of a random distribution of atoms, the elemental distribution in amorphous Zr59.3Cu28.8Al10.4Nb1.5 samples fabricated by laser powder bed fusion is analyzed. By comparison with the length scales of spatial isotope distributions, the probed volume of the bulk metallic glass shows a random distribution of all constitutional elements, and no evidence for clustering is observed. However, heat-treated metallic glass samples clearly exhibit elemental segregation which increases in size with annealing time. Segregations in Zr59.3Cu28.8Al10.4Nb1.5 > 1 nm can be observed and separated from random fluctuations, while accurate determination of segregations < 1 nm in size are limited by spatial resolution and detection efficiency.

Single scan STEM-EMCD in 3-beam orientation using a quadruple aperture.

The need to acquire multiple angle-resolved electron energy loss spectra (EELS) is one of the several critical challenges associated with electron magnetic circular dichroism (EMCD) experiments. If the experiments are performed by scanning a nanometer to atomic-sized electron probe on a specific region of a sample, the precision of the local magnetic information extracted from such data highly depends on the accuracy of the spatial registration between multiple scans. For an EMCD experiment in a 3-beam orientation, this means that the same specimen area must be scanned four times while keeping all the experimental conditions same. This is a non-trivial task as there is a high chance of morphological and chemical modification as well as non-systematic local orientation variations of the crystal between the different scans due to beam damage, contamination and spatial drift. In this work, we employ a custom-made quadruple aperture to acquire the four EELS spectra needed for the EMCD analysis in a single electron beam scan, thus removing the above-mentioned complexities. We demonstrate a quantitative EMCD result for a beam convergence angle corresponding to sub-nm probe size and compare the EMCD results for different detector geometries.

Biocompatibility of a Zr-Based Metallic Glass Enabled by Additive Manufacturing.

The present work explored the use of the selective laser melting (SLM) technique to develop a Zr-based bulk metallic glass (BMG) and investigate the influence of the process parameters on obtaining different levels of surface roughness. Moreover, the potential of the additively manufactured BMG Zr59.3Cu28.8Al10.4Nb1.5 (trade name AMLOY-ZR01) as an implant material was studied by evaluating the osteoblastic cell response to the alloy and its stability under simulated biological environments. The materials were characterized in terms of degree of crystallinity, surface roughness, and morphology, followed by a systematic investigation of the response of the MC3T3-E1 preosteoblastic cell line to the as-printed samples. The materials supported cell proliferation and differentiation of the preosteoblastic cells, with results comparable to the reference material Ti-6Al-4V. The surface microroughness and surface morphology (porous or groove-type laser tracks) investigated in this study did not have a significant effect on modulating the cell response. Ion release experiments showed a large increase in ion release under inflammatory conditions as compared to regular physiological conditions, which could be attributed to the increased local corrosion under inflammatory conditions. The findings in this work showed that the surface roughness of the additively manufactured BMG AMLOY-ZR01 can be tailored by controlling the laser power applied during the SLM process. The favorable cell response to the as-printed AMLOY-ZR01 represents of a significant advancement of the investigation of additively manufactured BMGs for orthopedic applications, while the results of the ion release study highlights the effect that inflammatory conditions could have on the degradation of the alloy.

Surface plasmons and magneto-optic activity in hexagonal Ni anti-dot arrays.

The influence of surface plasmons on the magneto-optic activity in a two-dimensional hexagonal array is addressed. The experiments were performed using hexagonal array of circular holes in a ferromagnetic Ni film. Well pronounced troughs are observed in the optical reflectivity, resulting from the presence of surface plasmons. The surface plasmons are found to strongly enhance the magneto-optic response (Kerr rotation), as compared to a continuous film of the same composition. The influence of the hexagonal symmetry of the pattern on the coupling between the plasmonic excitations is demonstrated, using optical diffraction measurements and theoretical calculations of the magneto-optic and of the angular dependence of the optical activity.

Simultaneous mapping of EMCD signals and crystal orientations in a transmission electron microscope.

When magnetic properties are analysed in a transmission electron microscope using the technique of electron magnetic circular dichroism (EMCD), one of the critical parameters is the sample orientation. Since small orientation changes can have a strong impact on the measurement of the EMCD signal and such measurements need two separate measurements of conjugate EELS spectra, it is experimentally non-trivial to measure the EMCD signal as a function of sample orientation. Here, we have developed a methodology to simultaneously map the quantitative EMCD signals and the local orientation of the crystal. We analyse, both experimentally and by simulations, how the measured magnetic signals evolve with a change in the crystal tilt. Based on this analysis, we establish an accurate relationship between the crystal orientations and the EMCD signals. Our results demonstrate that a small variation in crystal tilt can significantly alter the strength of the EMCD signal. From an optimisation of the crystal orientation, we obtain quantitative EMCD measurements.

The impact of number of repeats N on the interlayer exchange in [Formula: see text](001) superlattices.

The strength of the interlayer exchange coupling in [Fe/MgO][Formula: see text](001) superlattices with 2 ≤ N ≤ 10 depends on the number of bilayer repeats (N). The exchange coupling is antiferromagnetic for all the investigated thicknesses while being nine times larger in a sample with N = 4 as compared to N = 2. The sequence of the magnetic switching in two of the samples (N = 4, N = 8) is determined using polarized neutron reflectometry. The outermost layers are shown to respond at the lowest fields, consistent with having the weakest interlayer exchange coupling. The results are consistent with the existence of quantum well states defined by the thickness of the Fe and the MgO layers as well as the number of repeats (N) in [Fe/MgO][Formula: see text](001)superlattices.

Significance of self-trapping on hydrogen diffusion.

The diffusion rate of hydrogen in Nb was calculated using ab initio molecular dynamics simulations. At low temperatures the hydrogen is strongly trapped in a local strain field which is caused by the elastic response of the lattice. At elevated temperatures, the residence time (τ) of hydrogen in an interstitial site is not sufficient for fully developing the local strain field. This unbinding of the interstitial hydrogen and the strain field increases the hopping rate (1/τ) at elevated temperatures (>400 K). These results call for a revision of the conceptual framework of diffusion of hydrogen in transition metals at elevated temperatures.

The impact of nanoscale compositional variation on the properties of amorphous alloys.

The atomic distribution in amorphous FeZr alloys is found to be close to random, nevertheless, the composition can not be viewed as being homogenous at the nm-scale. The spatial variation of the local composition is identified as the root of the unusual magnetic properties in amorphous [Formula: see text] alloys. The findings are discussed and generalised with respect to the physical properties of amorphous and crystalline materials.

Quantitative EMCD by use of a double aperture for simultaneous acquisition of EELS.

The weak signal strength in electron magnetic circular dichroism (EMCD) measurements remains one of the main challenges in the quantification of EMCD related EELS spectra. As a consequence, small variations in peak intensity caused by changes of background intervals, choice of method for extraction of signal intensity and equally differences in sample quality can cause strong changes in the EMCD signal. When aiming for high resolution quantitative EMCD, an additional difficulty consists in the fact that the two angular resolved EELS spectra needed to obtain the EMCD signal are taken at two different instances and it cannot be guaranteed that the acquisition conditions for these two spectra are identical. Here, we present an experimental setup where we use a double hole aperture in the transmission electron microscope to obtain the EMCD signal in a single acquisition. This geometry allows for the parallel acquisition of the two electron energy loss spectra (EELS) under exactly the same conditions. We also compare the double aperture acquisition mode with the qE acquisition mode which has been previously used for parallel acquisition of EMCD. We show that the double aperture mode not only offers better signal to noise ratio as compared to qE mode but also allows for much higher acquisition times to significantly improve the signal quality which is crucial for quantitative analysis of the magnetic moments.

Ising-like behaviour of mesoscopic magnetic chains.

We demonstrate an experimental realization of the short range magnetic order in a one-dimensional Ising chain using fabricated mesospins. We confirm an excellent agreement between the experimental findings and simulations obtained using the original Ising model. In particular, we are able to show that the thermal behaviour of the mesoscopic Ising chain dominates over the thermal behaviour of the individual mesospins themselves, confirming that fabricated mesospins can be viewed as artificial magnetic atoms.

Dimensionality crossover in the induced magnetization of Pd layers.

The magnetic ordering of a series of samples consisting of ultrathin Fe layers embedded in Pd was investigated using the magneto-optical Kerr effect. The samples consisted of a single Fe layer with nominal thickness 0.2≤d(Fe)≤1.6 monolayers sandwiched between two 20 monolayer Pd layers. A dimensionality crossover from two dimensions to three dimensions occurs as d(Fe) is increased from 0.4 to 1.0 monolayers. First-principles calculations were performed in order to determine the magnetic profile, and we used a spin-wave quantum well model for obtaining a qualitative description of the dimensionality crossover. The results clearly prove the existence of a dimensionality crossover in the induced magnetization, opening new routes for addressing the influence of extension on order.

Concentration dependence of hydrogen diffusion in clamped vanadium (0 0 1) films.

The chemical diffusion coefficient of hydrogen in a 50 nm thin film of vanadium (0 0 1) is measured as a function of concentration and temperature, well above the known phase boundaries. Arrhenius analysis of the tracer diffusion constants reveal large changes in the activation energy with concentration: from 0.10 at 0.05 in H V-1 to 0.5 eV at 0.2 in H V-1. The results are consistent with a change from tetrahedral to octahedral site occupancy, in that concentration range. The change in site occupancy is argued to be caused by the uniaxial expansion of the film originating from the combined hydrogen induced expansion and the clamping of the film to the substrate.

Effect of uniaxial strain on the site occupancy of hydrogen in vanadium from density-functional calculations.

We investigate the influence of uniaxial strain on the site occupancy of hydrogen in vanadium, using density functional theory. The site occupancy is found to be strongly influenced by the strain state of the lattice. The results provide the conceptual framework for the atomistic description of the observed hysteresis in the to phase transition in bulk, as well as the preferred octahedral occupancy of hydrogen in strained V layers.

Quantitative analysis of magnetic spin and orbital moments from an oxidized iron (1 1 0) surface using electron magnetic circular dichroism.

Understanding the ramifications of reduced crystalline symmetry on magnetic behavior is a critical step in improving our understanding of nanoscale and interfacial magnetism. However, investigations of such effects are often controversial largely due to the challenges inherent in directly correlating nanoscale stoichiometry and structure to magnetic behavior. Here, we describe how to use Transmission Electron Microscope (TEM) to obtain Electron Magnetic Circular Dichroism (EMCD) signals as a function of scattering angle to locally probe the magnetic behavior of thin oxide layers grown on an Fe (1 1 0) surface. Experiments and simulations both reveal a strong dependence of the magnetic orbital to spin ratio on its scattering vector in reciprocal space. We exploit this variation to extract the magnetic properties of the oxide cladding layer, showing that it locally may exhibit an enhanced orbital to spin moment ratio. This finding is supported here by both spatially and angularly resolved EMCD measurements, opening up the way for compelling investigations into how magnetic properties are affected by nanoscale features.

Thermal fluctuations in artificial spin ice.

Artificial spin ice systems have been proposed as a playground for the study of monopole-like magnetic excitations, similar to those observed in pyrochlore spin ice materials. Currents of magnetic monopole excitations have been observed, demonstrating the possibility for the realization of magnetic-charge-based circuitry. Artificial spin ice systems that support thermal fluctuations can serve as an ideal setting for observing dynamical effects such as monopole propagation and as a potential medium for magnetricity investigations. Here, we report on the transition from a frozen to a dynamic state in artificial spin ice with a square lattice. Magnetic imaging is used to determine the magnetic state of the islands in thermal equilibrium. The temperature-induced onset of magnetic fluctuations and excitation populations are shown to depend on the lattice spacing and related interaction strength between islands. The excitations are described by Boltzmann distributions with their factors in the frozen state relating to the blocking temperatures of the array. Our results provide insight into the design of thermal artificial spin ice arrays where the magnetic charge density and response to external fields can be studied in thermal equilibrium.

Tailoring magnetism at the nanometer scale in SmCo5 amorphous films.

The thickness dependence of magnetic properties has been studied in SmCo5 amorphous films with imprinted in-plane anisotropy for thicknesses ranging down to the nanometer scale (2.5-100 nm). The field induced in-plane magnetic anisotropy decreases considerably when the film thickness is below 20 nm. Analysis of the magnetic anisotropy energy shows that the decrease of the induced in-plane anisotropy is accompanied by the development of an out-of-plane interface anisotropy. Two different regimes for the coercivity (Hc) change are found: below 3.75 nm, the Hc decreases continuously with decrease of the film thickness, whereas at above 3.75 nm, the Hc decreases with increase of the film thickness. This change in Hc can be understood by considering the decrease of the short range chemical order for the thinnest films (<3.75 nm) and the relative decrease of the interface contribution with increasing film thickness. The changes in anisotropy have a profound influence on the domain structure, in which the angle of the zigzag domain boundaries decreases with the inverse thickness of the layers.

Using light transmission to watch hydrogen diffuse.

Because of its light weight and small size, hydrogen exhibits one of the fastest diffusion rates in solid materials, comparable to the diffusion rate of liquid water molecules at room temperature. The diffusion rate is determined by an intricate combination of quantum effects and dynamic interplay with the displacement of host atoms that is still only partially understood. Here we present direct observations of the spatial and temporal changes in the diffusion-induced concentration profiles in a vanadium single crystal and we show that the results represent the experimental counterpart of the full time and spatial solution of Fick's diffusion equation. We validate the approach by determining the diffusion rate of hydrogen in a single crystal vanadium (001) film, with net diffusion in the [110] direction.

Hydrogen distribution in Nb/Ta superlattices.

The distribution of hydrogen in Nb/Ta superlattices has been investigated by combined neutron reflectivity and x-ray scattering. We provide evidence to support that strain modulations determined with x-ray diffraction can be interpreted as modulations in hydrogen content. We show that the hydrogen concentration is modulated and favors Nb, in agreement with previous studies. We measure the concentration directly using neutron reflectivity and demonstrate no detectable change in the distribution of hydrogen with temperature, in stark contrast to previous studies.