Artificial Graphene Spin Polarized Electrode for Magnetic Tunnel Junctions.

2D materials offer the ability to expose their electronic structure to manipulations by a proximity effect. This could be harnessed to craft properties of 2D interfaces and van der Waals heterostructures in devices and quantum materials. We explore the possibility to create an artificial spin polarized electrode from graphene through proximity interaction with a ferromagnetic insulator to be used in a magnetic tunnel junction (MTJ). Ferromagnetic insulator/graphene artificial electrodes were fabricated and integrated in MTJs based on spin analyzers. Evidence of the emergence of spin polarization in proximitized graphene layers was observed through the occurrence of tunnel magnetoresistance. We deduced a spin dependent splitting of graphene's Dirac band structure (∼15 meV) induced by the proximity effect, potentially leading to full spin polarization and opening the way to gating. The extracted spin signals illustrate the potential of 2D quantum materials based on proximity effects to craft spintronics functionalities, from vertical MTJs memory cells to logic circuits.

Identifying the Role of the Cationic Geometric Configuration in Spinel Catalysts for Polysulfide Conversion in Sodium-Sulfur Batteries.

An AB2X4 spinel structure, with tetrahedral A and octahedral B sites, is a paradigmatic class of catalysts with several possible geometric configurations and numerous applications, including polysulfide conversion in metal-sulfur batteries. Nonetheless, the influence of the geometric configuration and composition on the mechanisms of catalysis and the precise manner in which spinel catalysts facilitate the conversion of polysulfides remain unknown. To enable controlled exposure of single active configurations, herein, Cotd2+ and Cooh3+ in Co3O4 catalysts for sodium polysulfide conversion are in large part replaced by Fetd2+ and Feoh3+, respectively, generating FeCo2O4 and CoFe2O4. Through an examination of electrochemical activation energies, the characterization of symmetric cells, and theoretical calculations, we determine that Cooh3+ serves as the active site for the breaking of S-S bonds, while Cotd2+ functions as the active site for the formation of S-Na bonds. The current study underlines the subtle relationship between activity and geometric configurations of spinel catalysts, providing unique insights for the rational development of improved catalysts by optimizing their atomic geometric configuration.

Spin Effect to Promote Reaction Kinetics and Overall Performance of Lithium-Sulfur Batteries under External Magnetic Field.

Lithium-sulfur batteries (LSBs) are still limited by the shuttle of lithium polysulfides (LiPS) and the slow Li-S reaction. Herein, we demonstrate that when using cobalt sulfide as a catalytic additive, an external magnetic field generated by a permanent magnet can significantly improve the LiPS adsorption ability and the Li-S reaction kinetics. More specifically, the results show both experimentally and theoretically how an electron spin polarization of Co ions reduces electron repulsion and enhances the degree of orbital hybridization, thus resulting in LSBs with unprecedented performance and stability. Under an external magnetic field, LSBs with 0.0084 % per cycle decay rate at 2 C during 8150 cycles are produced. Overall, this work not only demonstrates an effective strategy to promote LiPS adsorption and electrochemical conversion in LSBs at no additional energy cost but also enriches the application of the spin effect in the electrocatalysis fields.

Evaluation of Sputtering Processes in Strontium Iridate Thin Films.

The growth of epitaxial thin films from the Ruddlesden-Popper series of strontium iridates by magnetron sputtering is analyzed. It was found that, even using a non-stoichiometric target, the films formed under various conditions were consistently of the perovskite-like n = ∞ SrIrO3 phase, with no evidence of other RP series phases. A detailed inspection of the temperature-oxygen phase diagram underscored that kinetics mechanisms prevail over thermodynamics considerations. The analysis of the angular distribution of sputtered iridium and strontium species indicated clearly different spatial distribution patterns. Additionally, significant backsputtering was detected at elevated temperatures. Thus, it is assumed that the interplay between these two kinetic phenomena is at the origin of the preferential nucleation of the SrIrO3 phase. In addition, strategies for controlling cation stoichiometry off-axis have also been explored. Finally, the long-term stability of the films has been demonstrated.

Implementing magnetically-active Sn-based nanocomposites in hexavalent chromium removal from drinking water.

A novel nanocomposite consisting of Fe3O4-loaded tin oxyhydroxy-chloride is demonstrated as an efficient adsorbent for the removal of hexavalent chromium in compliance to the new drinking water regulation. This study introduces a continuous-flow production of the nanocomposite through the separate synthesis of (i) 40 nm Fe3O4 nanoparticles and (ii) multilayered spherical arrangements of a tin hydroxy-chloride identified as abhurite, before the application of a wet-blending process. The homogeneous distribution of Fe3O4 nanoparticles on the abhurite's morphology, features nanocomposite with magnetic response whereas the 10 % loaded nanocomposite preserves a Cr(VI) uptake capacity of 7.2 mg/g for residual concentrations below 25 µg/L. Kinetic and thermodynamic examination of the uptake evolution indicates a relative rapid Cr(VI) capture dominated by interparticle diffusion and a spontaneous endothermic process mediated by reduction to Cr(III). The efficiency of the optimized nanocomposite was validated in a pilot unit operating in a sequence of a stirring reactor and a rotary magnetic separator showing an alternative and competitive application path than typical fixed-bed filtration, which is supported by the absence of any acute cellular toxicity according to human kidney cell viability tests.

Enhanced Oxygen Evolution and Zinc-Air Battery Performance via Electronic Spin Modulation in Heterostructured Catalysts.

Beyond optimizing electronic energy levels, the modulation of the electronic spin configuration is an effective strategy, often overlooked, to boost activity and selectivity in a range of catalytic reactions, including the oxygen evolution reaction (OER). This electronic spin modulation is frequently accomplished using external magnetic fields, which makes it impractical for real applications. Herein, spin modulation is achieved by engineering Ni/MnFe2O4 heterojunctions, whose surface is reconstructed into NiOOH/MnFeOOH during the OER. NiOOH/MnFeOOH shows a high spin state of Ni, which regulates the OH- and O2 adsorption energy and enables spin alignment of oxygen intermediates. As a result, NiOOH/MnFeOOH electrocatalysts provide excellent OER performance with an overpotential of 261 mV at 10 mA cm-2. Besides, rechargeable zinc-air batteries based on Ni/MnFe2O4 show a high open circuit potential of 1.56 V and excellent stability for more than 1000 cycles. This outstanding performance is rationalized using density functional theory calculations, which show that the optimal spin state of both Ni active sites and oxygen intermediates facilitates spin-selected charge transport, optimizes the reaction kinetics, and decreases the energy barrier to the evolution of oxygen. This study provides valuable insight into spin polarization modulation by heterojunctions enabling the design of next-generation OER catalysts with boosted performance.

Tuning the superconducting performance of YBa2Cu3O7-δ films through field-induced oxygen doping.

The exploration of metal-insulator transitions to produce field-induced reversible resistive switching effects has been a longstanding pursuit in materials science. Although the resistive switching effect in strongly correlated oxides is often associated with the creation or annihilation of oxygen vacancies, the underlying mechanisms behind this phenomenon are complex and, in many cases, still not clear. This study focuses on the analysis of the superconducting performance of cuprate YBa2Cu3O7-δ (YBCO) devices switched to different resistive states through gate voltage pulses. The goal is to evaluate the effect of field-induced oxygen diffusion on the magnetic field and angular dependence of the critical current density and identify the role of induced defects in the switching performance. Transition electron microscopy measurements indicate that field-induced transition to high resistance states occurs through the generation of YBa2Cu4O7 (Y124) intergrowths with a large amount of oxygen vacancies, in agreement with the obtained critical current density dependences. These results have significant implications for better understanding the mechanisms of field-induced oxygen doping in cuprate superconductors and their role on the superconducting performance.

Promoting Polysulfide Redox Reactions through Electronic Spin Manipulation.

Catalytic additives able to accelerate the lithium-sulfur redox reaction are a key component of sulfur cathodes in lithium-sulfur batteries (LSBs). Their design focuses on optimizing the charge distribution within the energy spectra, which involves refinement of the distribution and occupancy of the electronic density of states. Herein, beyond charge distribution, we explore the role of the electronic spin configuration on the polysulfide adsorption properties and catalytic activity of the additive. We showcase the importance of this electronic parameter by generating spin polarization through a defect engineering approach based on the introduction of Co vacancies on the surface of CoSe nanosheets. We show vacancies change the electron spin state distribution, increasing the number of unpaired electrons with aligned spins. This local electronic rearrangement enhances the polysulfide adsorption, reducing the activation energy of the Li-S redox reactions. As a result, more uniform nucleation and growth of Li2S and an accelerated liquid-solid conversion in LSB cathodes are obtained. These translate into LSB cathodes exhibiting capacities up to 1089 mA h g-1 at 1 C with 0.017% average capacity loss after 1500 cycles, and up to 5.2 mA h cm-2, with 0.16% decay per cycle after 200 cycles in high sulfur loading cells.

Electronic Spin Alignment within Homologous NiS2/NiSe2 Heterostructures to Promote Sulfur Redox Kinetics in Lithium-Sulfur Batteries.

The catalytic activation of the Li-S reaction is fundamental to maximize the capacity and stability of Li-S batteries (LSBs). Current research on Li-S catalysts mainly focuses on optimizing the energy levels to promote adsorption and catalytic conversion, while frequently overlooking the electronic spin state influence on charge transfer and orbital interactions. Here, hollow NiS2/NiSe2 heterostructures encapsulated in a nitrogen-doped carbon matrix (NiS2/NiSe2@NC) are synthesized and used as a catalytic additive in sulfur cathodes. The NiS2/NiSe2 heterostructure promotes the spin splitting of the 3d orbital, driving the Ni3+ transformation from low to high spin. This high spin configuration raises the electronic energy level and activates the electronic state. This accelerates the charge transfer and optimizes the adsorption energy, lowering the reaction energy barrier of the polysulfides conversion. Benefiting from these characteristics, LSBs based on NiS2/NiSe2@NC/S cathodes exhibit high initial capacity (1458 mAh·g⁻1 at 0.1C), excellent rate capability (572 mAh·g⁻1 at 5C), and stable cycling with an average capacity decay rate of only 0.025% per cycle at 1C during 500 cycles. Even at high sulfur loadings (6.2 mg·cm⁻2), high initial capacities of 1173 mAh·g⁻1 (7.27 mAh·cm⁻2) are measured at 0.1C, and 1058 mAh·g⁻1 is retained after 300 cycles.

Competing misfit relaxation mechanisms in epitaxial correlated oxides.

Strain engineering of functional properties in epitaxial thin films of strongly correlated oxides exhibiting octahedral-framework structures is hindered by the lack of adequate misfit relaxation models. Here we present unreported experimental evidence of a four-stage hierarchical development of octahedral-framework perturbations resulting from a progressive imbalance between electronic, elastic, and octahedral tilting energies in La(0.7)Sr(0.3)MnO(3) epitaxial thin films grown on SrTiO(3) substrates. Electronic softening of the Mn-O bonds near the substrate leads to the formation of an interfacial layer clamped to the substrate with strongly degraded magnetotransport properties, i.e., the so-called dead layer, while rigid octahedral tilts become relevant at advanced growth stages without significant effects on charge transport and magnetic ordering.

Spin-to-Charge Conversion in All-Oxide La2/3Sr1/3MnO3/SrIrO3 Heterostructures.

Spin injection and spin-charge conversion processes in all-oxide La2/3Sr1/3MnO3/SrIrO3 (LSMO/SIO) heterostructures with different SIO layer thickness and interfacial features have been studied. Ferromagnetic resonance (FMR) technique has been used to generate pure spin currents by spin pumping (SP) in ferromagnetic (FM) half-metallic LSMO. The change of the resonance linewidth in bare LSMO layers and LSMO/SIO heterostructures suggests a successful spin injection into the SIO layers. However, low values of the spin mixing conductance, compared to more traditional permalloy (Py)/Pt or yttrium iron garnet (YIG)/Pt systems, are found. A thorough analysis of the interfaces by high-resolution scanning transmission electron microscopy (HR-STEM) imaging suggests that they are structurally clean and atomic sharp, but a compositional analysis by energy-dispersive X-ray spectroscopy (EDS) reveals the interdiffusion of La, Ir, and Mn atomic species in the first atomic layers close to the interface. Inverse spin Hall effect (ISHE) measurements evidence that interfacial features play a very relevant role in controlling the effectiveness of the spin injection process and low transversal ISHE voltage signals are detected. In addition, it is found that larger voltage signals are detected for the lowest SIO layer thickness highlighting the role of the spin diffusion length (λsd)/SIO layer thickness ratio. The values of ISHE voltage are rather low but allow us to determine the spin Hall angle of SIO (θSH ≈ 1.12% at T = 250 K), which is remarkably similar to that obtained for the well-known Py/Pt system, therefore suggesting that SIO could be a promising spin-Hall material.

Tin Oxide Nanoparticles via Solar Vapor Deposition for Hexavalent Chromium Remediation.

Tin oxide nanoparticles optimized to capture low concentrations of hexavalent chromium from water were developed through a facile, scalable, and low-cost one-step solar vapor deposition methodology. Considering the preservation of high electron donation capacity as the key to support the reduction of mobile Cr(VI) into insoluble forms, the growth of SnO nanoparticles was favored by the co-evaporation of SnO2 with Fe powders at various mass ratios. Characterization techniques indicated that the percentage and the stability of SnO is proportional to the Fe content in the target with a requirement of at least 50% wt to inhibit the formation of a passive SnO2 surface layer. The produced particles were evaluated regarding their efficiency to capture Cr(VI) under conditions similar to water treatment for drinking purposes (pH 7). It was revealed that passivation-free SnO nanoparticles deliver significant improvement in the adsorption capacity corresponding to the residual concentration of 25 µg/L, reaching a value of 1.74 mg/g for the sample prepared with 50% wt Fe in the target. The increase of water acidity was found responsible for the activation of more reduction sites on the particle surface, as reflected through the elevation of efficiency by more than 20% at pH 6.

Sulfate-Decorated Amorphous-Crystalline Cobalt-Iron Oxide Nanosheets to Enhance O-O Coupling in the Oxygen Evolution Reaction.

The electrochemical oxygen evolution reaction (OER) plays a fundamental role in several energy technologies, which performance and cost-effectiveness are in large part related to the used OER electrocatalyst. Herein, we detail the synthesis of cobalt-iron oxide nanosheets containing controlled amounts of well-anchored SO42- anionic groups (CoFexOy-SO4). We use a cobalt-based zeolitic imidazolate framework (ZIF-67) as the structural template and a cobalt source and Mohr's salt ((NH4)2Fe(SO4)2·6H2O) as the source of iron and sulfate. When combining the ZIF-67 with ammonium iron sulfate, the protons produced by the ammonium ion hydrolysis (NH4+ + H2O = NH3·H2O + H+) etch the ZIF-67, dissociating its polyhedron structure, and form porous assemblies of two-dimensional nanostructures through a diffusion-controlled process. At the same time, iron ions partially replace cobalt within the structure, and SO42- ions are anchored on the material surface by exchange with organic ligands. As a result, ultrathin CoFexOy-SO4 nanosheets are obtained. The proposed synthetic procedure enables controlling the amount of Fe and SO4 ions and analyzing the effect of each element on the electrocatalytic activity. The optimized CoFexOy-SO4 material displays outstanding OER activity with a 10 mA cm-2 overpotential of 268 mV, a Tafel slope of 46.5 mV dec-1, and excellent stability during 62 h. This excellent performance is correlated to the material's structural and chemical parameters. The assembled nanosheet structure is characterized by a large electrochemically active surface area, a high density of reaction sites, and fast electron transportation. Meanwhile, the introduction of iron increases the electrical conductivity of the catalysts and provides fast reaction sites with optimum bond energy and spin state for the adsorption of OER intermediates. The presence of sulfate ions at the catalyst surface modifies the electronic energy level of active sites, regulates the adsorption of intermediates to reduce the OER overpotential, and promotes the surface charge transfer, which accelerates the formation of oxygenated intermediates. Overall, the present work details the synthesis of a high-efficiency OER electrocatalyst and demonstrates the introduction of nonmetallic anionic groups as an excellent strategy to promote electrocatalytic activity in energy conversion technologies.

Suppression of spin rectification effects in spin pumping experiments.

Spin pumping (SP) is a well-established method to generate pure spin currents allowing efficient spin injection into metals and semiconductors avoiding the problem of impedance mismatch. However, to disentangle pure spin currents from parasitic effects due to spin rectification effects (SRE) is a difficult task that is seriously hampering further developments. Here we propose a simple method that allows suppressing SRE contribution to inverse spin Hall effect (ISHE) voltage signal avoiding long and tedious angle-dependent measurements. We show an experimental study in the well-known Py/Pt system by using a coplanar waveguide (CPW). Results obtained demonstrate that the sign and size of the measured transverse voltage signal depends on the width of the sample along the CPW active line. A progressive reduction of this width evidences that SRE contribution to the measured transverse voltage signal becomes negligibly small for sample width below 200 µm. A numerical solution of the Maxwell equations in the CPW-sample setup, by using the Landau-Lifshitz equation with the Gilbert damping term (LLG) as the constitutive equation of the media, and with the proper set of boundary conditions, confirms the obtained experimental results.

X-ray Absorption Spectroscopy Study of Thickness Effects on the Structural and Magnetic Properties of Pr2-δNi1-xMn1+xO6-y Double Perovskite Thin Films.

In this work, we report a systematic study of the influence of film thickness on the structural and magnetic properties of epitaxial thin films of Pr2-δNi1-xMn1+xO6-y (PNMO) double perovskite grown on top of two different (001)-SrTiO3 and (001)-LaAlO3 substrates by RF magnetron sputtering. A strong dependence of the structural and magnetic properties on the film thickness is found. The ferromagnetic transition temperature (TC) and saturation magnetization (Ms) are found to decrease when reducing the film thickness. In our case, the thinnest films show a loss of ferromagnetism at the film-substrate interface. In addition, the electronic structure of some characteristic PNMO samples is deeply analyzed using X-ray absorption spectroscopy (XAS) and X-ray magnetic circular dichroism (XMCD) measurements and compared with theoretical simulations. Our results show that the oxidation states of Ni and Mn ions are stabilized as Ni2+ and Mn4+, thus the ferromagnetism is mainly due to Ni2+-O-Mn4+ superexchange interactions, even in samples with poor ferromagnetic properties. XMCD results also make evident large variations on the spin and orbital contributions to the magnetic moment as the film's thickness decreases.

Optimization of the Growth Process of Double Perovskite Pr2-δNi1-xMn1+xO6-y Epitaxial Thin Films by RF Sputtering.

Epitaxial thin films of Pr2-δNi1-xMn1+xO6-y (PNMO) double perovskite were grown on (001)-oriented SrTiO3 substrates by RF magnetron sputtering. The influence of the growth parameters (oxygen pressure, substrate temperature, and annealing treatments) on the structural, magnetic and transport properties, and stoichiometry of the films was thoroughly investigated. It is found that high-quality epitaxial, insulating, and ferromagnetic PNMO thin films can only be obtained in a narrow deposition parameter window. It is shown that a careful selection of the growth conditions allows for obtaining a high degree of Ni/Mn cation ordering, which is reflected in the values of the Curie temperature, TC, and saturation magnetization, MS, which are very close to those of bulk material.

Formation of Nickel Oxide Nanocuboids in Ferromagnetic La2Ni1-xMn1+xO6.

The control of the spontaneous formation of nanostructures at the surface of thin films is of strong interest in many different fields, from catalysts to microelectronics, because surface and interfacial properties may be substantially enhanced. Here, we analyze the formation of nickel oxide nanocuboids on top of La2Ni1-xMn1+xO6 double perovskite ferromagnetic thin films, epitaxially grown on SrTiO3 (001) substrates by radio-frequency (RF) magnetron sputtering. We show that, by annealing the films at high temperature under high oxygen partial pressure, the spontaneous segregation of nanocuboids is enhanced. The evolution of the structural and magnetic properties of the films is studied as a function of the annealing treatments at different temperatures. It is shown that the formation of NiOx nanocuboids leads to a nanostructured film surface with regions of locally different electrical transport characteristics.

Hydrotalcite-Embedded Magnetite Nanoparticles for Hyperthermia-Triggered Chemotherapy.

A magnetic nanocomposite, consisting of Fe3O4 nanoparticles embedded into a Mg/Al layered double hydroxide (LDH) matrix, was developed for cancer multimodal therapy, based on the combination of local magnetic hyperthermia and thermally induced drug delivery. The synthesis procedure involves the sequential hydrolysis of iron salts (Fe2+, Fe3+) and Mg2+/Al3+ nitrates in a carbonate-rich mild alkaline environment followed by the loading of 5-fluorouracil, an anionic anticancer drug, in the interlayer LDH space. Magnetite nanoparticles with a diameter around 30 nm, dispersed in water, constitute the hyperthermia-active phase able to generate a specific loss of power of around 500 W/g-Fe in an alternating current (AC) magnetic field of 24 kA/m and 300 kHz as determined by AC magnetometry and calorimetric measurements. Heat transfer was found to trigger a very rapid release of drug which reached 80% of the loaded mass within 10 min exposure to the applied field. The potential of the Fe3O4/LDH nanocomposites as cancer treatment agents with minimum side-effects, owing to the exclusive presence of inorganic phases, was validated by cell internalization and toxicity assays.

Dipolar driven spontaneous self assembly of superparamagnetic Co nanoparticles into micrometric rice-grain like structures.

Superparamagnetic single crystal single domain Co nanoparticles of 6 nm in diameter evaporated onto highly pyrolytic oriented graphite spontaneously self-assemble into super structures with an elongated shape. These structures have been studied by optical and scanning electron microscopies, atomic and magnetic force microscopy, electron dispersive X-ray analysis, and SQUID magnetometry. We propose that the weak dipolar interactions between superparamagnetic dipoles of the cobalt nanoparticles are responsible for the formation of these structures when the dipolar magnetic interactions are strong enough to influence the general process of self-assembly dominated by van der Waals forces between neighboring nanoparticles and between nanoparticles and the substrate during evaporation of the solvent.

Self-assembled multifunctional Fe/MgO nanospheres for magnetic resonance imaging and hyperthermia.

A one-step process for the production of nanoparticles presenting advanced magnetic properties can be achieved using vapor condensation. In this article, we report on the fabrication of Fe particles covered by a uniform MgO epitaxial shell. MgO has a lower surface energy than Fe, which results in a core-shell crystal formation. The particles satisfy a few of technical requirements for the practical use in real clinics, such as a high biocompatibility in living cells in-vitro, an injection through blood vessels without any clothing problems in murine model, a high absorption rate for magnetic hyperthermia at small particle concentration, and the potential to be used as contrast agent in the field of diagnostic magnetic imaging. They are also able to be used in drug delivery and magnetic-activated cell sorting. FROM THE CLINICAL EDITOR: In this paper, the authors report on the synthesis of Fe particles covered by a uniform MgO epitaxial shell resulting in a core-shell crystal formation. The particles are proven to be useful as contrast agents for magnetic resonance imaging and have the potential to be useful as heating mediators for cancer therapy through hyperthermia. They also might be used in drug delivery and magnetic-activated cell sorting.