Dimensionality Engineering of Magnetic Anisotropy from the Anomalous Hall Effect in Synthetic SrRuO3 Crystals.

Magnetic anisotropy in atomically thin correlated heterostructures is essential for exploring quantum magnetic phases for next-generation spintronics. Whereas previous studies have mostly focused on van der Waals systems, here we investigate the impact of dimensionality of epitaxially grown correlated oxides down to the monolayer limit on structural, magnetic, and orbital anisotropies. By designing oxide superlattices with a correlated ferromagnetic SrRuO3 and nonmagnetic SrTiO3 layers, we observed modulated ferromagnetic behavior with the change of the SrRuO3 thickness. Especially, for three-unit-cell-thick layers, we observe a significant 1500% improvement of the coercive field in the anomalous Hall effect, which cannot be solely attributed to the dimensional crossover in ferromagnetism. The atomic-scale heterostructures further reveal the systematic modulation of anisotropy for the lattice structure and orbital hybridization, explaining the enhanced magnetic anisotropy. Our findings provide valuable insights into engineering the anisotropic hybridization of synthetic magnetic crystals, offering a tunable spin order for various applications.

Enhanced Photothermal Effect Assisted by Resonance Energy Transfer in Carbon/Covellite Core-Shell Nanoparticles toward a High-Performance Interfacial Water Evaporation Process.

Carbon and semiconductor nanoparticles are promising photothermal materials for various solar-driven applications. Inevitable recombination of photoinduced charge carriers in a single constituent, however, hinders the realization of a greater photothermal effect. Core-shell heterostructures utilizing the donor-acceptor pair concept with high-quality interfaces can inhibit energy loss from the radiation relaxation of excited species, thereby enhancing the photothermal effect. Here, core-shell structures composed of a covellite (CuS) shell (acceptor) and spherical carbon nanoparticle (CP) core (donor) (abbreviated as CP/CuS) are proposed to augment the photothermal conversion efficiency via the Förster resonance energy transfer (FRET) mechanism. The close proximity and spectral overlap of the donor and acceptor trigger the FRET mechanism, where the electronic excitation relaxation energy of the CP reinforces the plasmonic resonance and near-infrared absorption in CuS, resulting in boosting the overall photothermal conversion efficiency. CP/CuS core-shell coated on polyurethane (PU) foam exhibits a total solar absorption of 97.1%, leading to an elevation in surface temperature of 61.6 °C in dry conditions under simulated solar illumination at a power density of 1 kW m-2 (i.e., 1 sun). Leveraging the enhanced photothermal conversion emanated from the energy transfer effect in the core-shell structure, CP/CuS-coated PU foam achieves an evaporation rate of 1.62 kg m-2 h-1 and an energy efficiency of 93.8%. Thus, amplifying photothermal energy generation in core-shell structures via resonance energy transfer can be promising in solar energy-driven applications and thus merits further exploration.

Exotic Magnetic Anisotropy Near Digitized Dimensional Mott Boundary.

The magnetic anisotropy of low-dimensional Mott systems exhibits unexpected magnetotransport behavior useful for spin-based quantum electronics. Yet, the anisotropy of natural materials is inherently determined by the crystal structure, highly limiting its engineering. The magnetic anisotropy modulation near a digitized dimensional Mott boundary in artificial superlattices composed of a correlated magnetic monolayer SrRuO3 and nonmagnetic SrTiO3 , is demonstrated. The magnetic anisotropy is initially engineered by modulating the interlayer coupling strength between the magnetic monolayers. Interestingly, when the interlayer coupling strength is maximized, a nearly degenerate state is realized, in which the anisotropic magnetotransport is strongly influenced by both the thermal and magnetic energy scales. The results offer a new digitized control for magnetic anisotropy in low-dimensional Mott systems, inspiring promising integration of Mottronics and spintronics.

Optimizing calcium materials for minimizing arsenate phytoavailability in upland arable soil based on geochemical analysis.

This study aimed to evaluate the reducing effects of calcite and phosphogypsum on arsenate [As(V)] availability to plants and elucidate the mechanisms of As(V) immobilization. The concentration of available As(V) to plants in upland arable soils with 1% calcite and phosphogypsum decreased to 17.4% and 36.9%, respectively, compared to the control. As(V) phytoavailability depends on the soil pH and calcium materials. The process of stabilizing As(V) (F3; anion exchange) with phosphogypsum is faster and easier compared to that with calcite (F4; bind to carbonate), but it results in a less stable form. New Ca-As(V) minerals (Ca52(HAsO4)x(AsO4)∙yH2O, Ca5H2x(AsO4)∙yH2O, or Ca32(AsO4)∙10 H2O) were identified in X-ray diffraction (XRD) patterns with calcite treatment. Precipitation, the primary mechanism induced by calcite, was activated at a soil pH above 8.0. Based on the deconvolution of calcium and sulfur X-ray photoelectron spectroscopy spectra and the peak shift in the XRD pattern in phosphogypsum, the substitution in which SO42- is exchanged with HAsO42- is the primary mechanism for As(V) immobilization. Substitution induced by phosphogypsum is a suitable reaction in upland arable soils, the predominant form of As(V) in the soil, with a pH range of 5-7.

Atomic-Scale Modulation of Synthetic Magnetic Order in Oxide Superlattices.

Atomic-scale precision control of magnetic interactions facilitates a synthetic spin order useful for spintronics, including advanced memory and quantum logic devices. Conventional modulation of synthetic spin order has been limited to metallic heterostructures that exploit Ruderman-Kittel-Kasuya-Yosida interaction through a nonmagnetic metallic spacer; however, they face issues arising from Joule heating and/or electric breakdown. The practical realization and observation of a synthetic spin order across a nonmagnetic insulating spacer will lead to the development of spin-related devices with a completely different concept. Herein, the atomic-scale modulation of the synthetic spiral spin order in oxide superlattices composed of ferromagnetic metal and nonmagnetic insulator layers is reported. The atomically controlled superlattice exhibits an oscillatory magnetic behavior, representing the existence of a spiral spin structure. Depth-sensitive polarized neutron reflectometry evidences modulated spiral spin structures as a function of the nonmagnetic insulator layer thickness. Atomic-scale customization of the spin state can move the field one step further to actual spintronic applications.

Emergent Topological Hall Effect from Exchange Coupling in Ferromagnetic Cr2Te3/Noncoplanar Antiferromagnetic Cr2Se3 Bilayers.

The topological Hall effect has been observed in magnetic materials of complex spin structures or bilayers of trivial magnets and strong spin-orbit-coupled systems. In view of current attention on dissipationless topological electronics, the occurrence of the topological Hall effect in new systems or by an unexpected mechanism is fascinating. Here, we report a robust topological Hall effect generated in bilayers of a ferromagnet and a noncoplanar antiferromagnet, from the interfacial Dzyaloshinskii-Moriya interaction due to the exchange coupling of magnetic layers. Molecular beam epitaxy has been utilized to fabricate heterostructures of a ferromagnetic metal Cr2Te3 and a noncoplanar antiferromagnet Cr2Se3. A significant topological Hall effect at low temperature implies the development of nontrivial spin chirality, and density functional theory calculations explain the correlation of the Dzyaloshinskii-Moriya interaction increase and inversion symmetry breaking at the interface. The presence of noncoplanar ordering in the antiferromagnet plays a pivotal role in producing the topological Hall effect. Our results suggest that the exchange coupling in ferromagnet/noncoplanar antiferromagnet bilayers could be an alternative mechanism toward topologically protected magnetic structures.

Octahedral Symmetry Modification Induced Orbital Occupancy Variation in VO2.

Octahedral symmetry is one of the parameters to tune the functional properties of complex oxides. VO2, a complex oxide with a 3d1 electronic system, exhibits an insulator-metal transition (IMT) near room temperature (∼68 °C), accompanying a change in the octahedral structure from asymmetrical to symmetrical. However, the role of octahedral symmetry in VO2 on the IMT characteristics is unclear. Crystal and electronic structure analyses combined with density-functional-theory calculations showed the bandwidth-controlled IMT characteristics of monoclinic VO2 with high octahedral symmetry. The expanded apical V-O length for a high octahedral symmetry of a VO2 film increased the bandwidth of the conduction band by depressing V 3d-O 2p hybridization. As a result, the interdimer hopping energy increased and thereby decreased the IMT temperature, although the short V-V chain enhanced electron correlation. These findings suggest that octahedral symmetry can control the IMT characteristics of VO2 by changing the orbital occupancy.

One-pot synthesis of Ag-Cu-Cu2O/C nanocomposites derived from a metal-organic framework as a photocatalyst for borylation of aryl halide.

Mixed metal-metal oxide/C (Ag-Cu-Cu2O/C) nanocomposites were synthesized by the heat treatment of a metal-organic framework under a N2 flow using the one-pot synthesis method. The as-prepared nanocomposites were characterized using a range of techniques, such as TEM, elemental mapping, XRD, N2 sorption, UV-Vis DRS, and XPS. The nanoparticles were successfully formed with high dispersion in porous carbon materials and high crystallinity based on the analysis results. The Ag-Cu-Cu2O/C nanocomposites (35 nm) showed high photocatalytic activity and good recyclability toward the borylation of aryl halides under a xenon arc lamp. This result can enhance the interest in photocatalysis for various applications, particularly in organic reactions, using a simple and efficient synthesis method.

Efficient photocatalytic degradation of dyes using photo-deposited Ag nanoparticles on ZnO structures: simple morphological control of ZnO.

In this work, morphology-controlled ZnO structures were prepared via a hydrothermal method by simple adjustments in the NaOH concentration. The NaOH concentration variation from 0.2 to 1.2 M resulted in the formation of ZnO structures in shapes such as walnut, spherical flower, flower, rod, and urchin-like. The extent of OH- ions is the main factor influencing the growth of ZnO structures. Well-defined morphologies, good crystallinity, and optical properties were obtained for all ZnO structures. Among these ZnO structures, ZnOsf (spherical flower-like) structure showed a greater percentage of photodegradation of methyl orange and rhodamine B dyes. Surface plasmon resonance was achieved by modifying the surface of ZnO with Ag nanoparticles. ZnOsf was loaded with Ag nanoparticles by a facile photo-deposition method. Ag-ZnOsf showed superior photoactivity and recyclability for the degradation of methyl orange and rhodamine B. Therefore, modification of different ZnO structures can help realize potential catalysts for future environmental applications.

Understanding the Phase Transition Evolution Mechanism of Partially M2 Phased VO2 Film by Hydrogen Incorporation.

Studies on the hydrogen incorporated M1 phase of VO2 film have been widely reported. However, there are few works on an M2 phase of VO2. Recently, the M2 phase in VO2 has received considerable attention due to the possibility of realizing a Mott transition field-effect transistor. By varying the postannealing environment, systematic variations of the M2 phase in (020)-oriented VO2 films grown on Al2O3(0001) were observed. The M2 phase converted to the metallic M1 phase at first and then to the metallic rutile phase after hydrogen annealing (i.e., for H2/N2 mixture and H2 environments). From the diffraction and spectroscopy measurements, the transition is attributed to suppressed electron interactions, not structural modification caused by hydrogen incorporation. Our results suggest the understanding of the phase transition process of the M2 phase by hydrogen incorporation and the possibility of realization of the M2 phased-based Mott transition field-effect transistor.

Propagation Control of Octahedral Tilt in SrRuO3 via Artificial Heterostructuring.

Bonding geometry engineering of metal-oxygen octahedra is a facile way of tailoring various functional properties of transition metal oxides. Several approaches, including epitaxial strain, thickness, and stoichiometry control, have been proposed to efficiently tune the rotation and tilt of the octahedra, but these approaches are inevitably accompanied by unnecessary structural modifications such as changes in thin-film lattice parameters. In this study, a method to selectively engineer the octahedral bonding geometries is proposed, while maintaining other parameters that might implicitly influence the functional properties. A concept of octahedral tilt propagation engineering is developed using atomically designed SrRuO3/SrTiO3 (SRO/STO) superlattices. In particular, the propagation of RuO6 octahedral tilt within the SRO layers having identical thicknesses is systematically controlled by varying the thickness of adjacent STO layers. This leads to a substantial modification in the electromagnetic properties of the SRO layer, significantly enhancing the magnetic moment of Ru. This approach provides a method to selectively manipulate the bonding geometry of strongly correlated oxides, thereby enabling a better understanding and greater controllability of their functional properties.

Ultrasensitive detection of hydrogen peroxide and dopamine using copolymer-grafted metal-organic framework based electrochemical sensor.

We reported the synthesis of a copolymer- and metal-organic framework-based electrochemical sensor, UiO-66-NH2@P(ANI-co-ANA) using the polymerization method for the highly sensitive and selective detection of hydrogen peroxide (H2O2) and dopamine (DA). The as-synthesized material was characterized via Fourier transform infrared spectroscopy, X-ray diffraction analysis, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, and thermogravimetric analysis. The electrochemical characteristics of the proposed sensor were evaluated via impedance spectroscopy and cyclic voltammetry (CV). The electrochemical oxidation of DA and the reduction of H2O2 were determined via CV, square-wave voltammetry, and chronoamperometric techniques. The fabricated sensor exhibited a wide linear range of 25-500 µM, with a sensitivity of 1396.1 µAµM-1cm-2 and a limit of detection of 0.6 µM, for the electrochemical reduction of H2O2. Additionally, it exhibited a wide linear range of 10-110 µM, with a sensitivity of 1110.2 µAµM-1cm-2 and a limit of detection of 0.3 µM, for the electrochemical detection of DA. The practical utility of the fabricated sensor was evaluated via the detection of H2O2 in milk samples and DA in human urine samples.