Copper-based charge transfer multiferroics with a d9d^9 configuration

Multiferroics are materials with a coexistence of magnetic and ferroelectric order allowing the manipulation of magnetism by applications of an electric field through magnetoelectric coupling effects. Here we propose an idea to design a class of multiferroics with a $d^9$ configuration using the magnetic order in copper-oxygen layers appearing in copper oxide high-temperature superconductors by inducing ferroelectricity. Copper-based charge transfer multiferroics SnCuO2 and PbCuO2 having the inversion symmetry breaking $P4mm$ polar space group are predicted to be such materials. The active inner s electrons in Sn and Pb hybridize with O $2p$ states leading the buckling in copper-oxygen layers and thus induces ferroelectricity, which is known as the lone pair mechanism. As a result of the $d^9$ configuration, SnCuO2 and PbCuO2 are charge transfer insulators with the antiferromagnetic ground state of the moment on Cu retaining some strongly correlated physical properties of parent compounds of copper oxide high-temperature superconductors. Our work reveals the possibility of designing multiferroics based on copper oxide high-temperature superconductors.Comment: 18 pages, 5 figures, 1 tabl

Elemental topological ferroelectrics and polar metals of few-layer materials

Ferroelectricity can exist in elemental phases as a result of charge transfers between atoms occupying inequivalent Wyckoff positions. We investigate the emergence of ferroelectricity in two-dimensional elemental materials with buckled honeycomb lattices. Various multi-bilayer structures hosting ferroelectricity are designed by stacking-engineering. Ferroelectric materials candidates formed by group IV and V elements are predicted theoretically. Ultrathin Bi films show layer-stacking-dependent physical properties of ferroelectricity, topology, and metallicity. The two-bilayer Bi film with a polar stacking sequence is found to be an elemental topological ferroelectric material. Three and four bilayers Bi films with polar structures are ferroelectric-like elemental polar metals with topological nontrivial edge states. For Ge and Sn, trivial elemental polar metals are predicted. Our work reveals the possibility of design two-dimensional elemental topological ferroelectrics and polar metals by stacking-engineering.Comment: 18 pages, 6 figure

Ultrastable sodium metal plating/striping by engineering heterogeneous nucleation on TiO2 nanotube arrays

Sodium metal is considered as an excellent anode material for sodium-based energy storage devices with both high energy density and low cost, but the uncontrollable growth of sodium metal seriously limits its application. Herein, we firstly propose 3D spaced TiO2 nanotube arrays (STNTs) uniformly coated with ultra-fine metal (Ag, Cu) nanocrystals as a substrate with absorption-diffusion regulation strategy to control the sodium metal deposition behavior. TiO2 has a higher sodiophilic activity with larger Na absorption energy than the traditional copper substrate. Moreover, it is found by ab initio molecular dynamics (AIMD) simulations that it is much easier for Na to spread upon the surface of silver compared to copper, and thus forming a mixed Na-Ag layer at the interface. As a result, sodium metal is inclined to deposit inside or along the nanotube in STNTs-Ag in nanoscale. Finally, STNTs-Ag||Na half-cell displays a high Coulombic efficiency ~99.5% even after 500 cycles with 1 mAh cm(-2). Symmetric cell of STNTs-Ag-Na exhibits an ultralow overpotential of 4 mV and a long-term cycling life over 1400 h. Moreover, STNTs-Ag-Na anode coupling with Na3V2(PO4)(3) cathode exhibits a significantly reduced polarization voltage with 22 mV and improved rate performance with 110 mAhg(-1) at 10 C

Spin-wave modes of elliptical skyrmions in magnetic nanodots

Magnetic skyrmions, whose shapes are ellipse due to the presence of anisotropic Dzyaloshinskii–Moriya interaction (DMI), have already been discovered in experiments recently. By using micromagnetic simulations, we discuss the ground state and the spin-wave modes of a single elliptical skyrmion in a confined nanodot. It is found that the shapes of skyrmion are stretched into a horizontal ellipse, vertical ellipse, or stripe shape under different strengths of anisotropic DMI. When elliptical skyrmions are excited by in-plane ac magnetic fields, the spin-wave mode contains a counterclockwise rotation mode at high frequencies and a clockwise (CW) rotation mode at low frequencies, and the CW mode depends on the strength of anisotropic DMI. When elliptical skyrmions are excited by out-of-plane ac magnetic fields, the spin-wave mode is split from a simple breathing mode into two complex breathing modes, including a mixed mode of CW rotation and breathing, and another anisotropic breathing mode. Our results provide an understanding of the rich spin-wave modes for skyrmions, which may contribute to the applications in magnonics

Cation-deficient TiO2(B) nanowires with protons charge compensation for regulating reversible magnesium storage

Magnesium battery is a recently emerging energy storage system that has attracted considerable attention. However, its development is limited by the lack of proper electrode materials for reversible Mg2+ intercalation/de-intercalation with satisfied capacity. Here, we firstly report easy synthesis of Ti-deficient bronze titanium dioxide nanowires by topology transformation of H-titanate precursor. It's found OH anions substitution of O2- supports the formation of Ti vacancies in TiO2(B) with a high concentration, denoted as (Ti0.91O1.64(OH)(0.36)), and can be utilized as a robust host for Mg-ion storage. Both the theoretical and experimental study revealed that Ti-deficient TiO2(B) exhibits much improved electronic properties with unpaired electrons. Density functional theory (DFT) calculations also reveal Ti vacancies provide more feasible binding sites for Mg-ion. More importantly, it's surprisingly found the presence of protons enables a suitable binding energy for Mg-ion intercalation and extraction. As a result, such material displays discharge and charge capacities of 217.3 and 165.3 mA h g(-1) at 0.02 A g(-1), representing the highest value among the reported Ti-based electrode materials as well as a high initial Columbic efficiency up to 76.1%. This study gives a new and in-depth view on how cation-deficient structure regulates and promotes the reversible energy storage

Spin field-effect transistors based on massless birefringent Dirac fermions in polar Dirac semimetals

The Datta-Das-type spin field-effect transistor, using a two-dimensional electron gas in a semiconductor heterostructure as a channel, plays a key role in spintronics. Here, we theoretically present a type of spin field-effect transistor based on massless birefringent Dirac fermions in polar Dirac semimetals. The manipulation of spin arises from the existence of the strong spin-orbit coupling, polar space groups, and Dirac cones in a single phase. The oscillatory channel conductance can be controlled by the sign of gate voltage in addition to its magnitude due to the gapless band structures of polar Dirac semimetals. Such spin field-effect transistor provides guidance for the further design of spintronic devices.Comment: 14 pages, 3 figure

Understanding the mechanism of byproduct formation with in operando synchrotron techniques and its effects on the electrochemical performance of VO 2 (B) nanoflakes in aqueous rechargeable zinc batteries

Monoclinic VO$_2$(B) nanoflakes prepared by a hydrothermal method displayed superior electrochemical performance in 1 M ZnSO$_4$ electrolyte. The reaction mechanisms of VO$_2$(B) and the essential causes of byproduct formation in aqueous rechargeable zinc batteries (ARZBs) were comprehensively studied by electrochemical measurements combined with in operando synchrotron techniques and first-principles calculations. During the electrochemical processes, the electrode underwent a reversible solid-solution reaction between VO$_2$(B) and Zn$_{0.44}$VO$_2$ with the simultaneous formation/decomposition of the (Zn(OH)$_2$)$_3$(ZnSO$_4$)·5H$_2$O byproduct. Importantly, the formation of the byproduct was attributed to [Zn(H$_2$O)$_6$]$^{2+}$ dehydration, where the byproduct could protect the electrode material from the corrosion of H$_3$O$^+$ and facilitate the dehydration process of Zn$^{2+}$ on the electrode–electrolyte interface. The byproducts could facilitate the migration of Zn$^{2+}$ on the electrode surface due to their three-dimensional pathways. In addition, the electrochemical performance of VO$_2$(B) and the byproduct in ZnSO$_4$ electrolyte were compared with those in Zn(CF$_3$SO$_3$)$_2$ and Zn(NO$_3$)$_2$. An appropriate electrolyte (1 M Zn(CF$_3$SO$_3$)$_2$) to form a byproduct with largely expanded ionic pathways was proven to further improve the electrochemical performance of VO$_2$(B). This work not only provides a deep understanding of the Zn$^{2+}$ storage mechanism in VO$_2$(B) but also establishes a clear relationship between the byproducts and electrochemical performance of vanadium-based electrode materials in ARZBs

Understanding 2D Semiconductor Edges by Combining Local and Nonlocal Effects: The Case of MoSi₂N₄

Similar to surfaces of three-dimensional (3D) bulk materials, edges are inevitable in 2D materials and have been studied a lot (e.g., for MoS2). In the current work, taking the ambient-stable MoSi2N4 as an example, nonpolar and polar edges as well as polar-edge reconstructions are studied based on first-principles calculations. We demonstrate that a combination of the “local” electron counting model (ECM) at edges and “nonlocal” charge polarity analysis (CPA) across the ribbon is essential for a unified understanding of the “local” edge properties and edge reconstructions in the following aspects. For pristine edges, the semiconducting (metallic) property of nonpolar armchair (polar zigzag) edges is related to CPA, and the spin-paired (spin-polarized) electronic structure of nonpolar (polar) edges is related to the ECM. For polar-edge reconstructions: (1) the polar edges become semiconducting when the reversed dipole from edge-reconstruction partially cancels the accumulated electric dipole within the ribbon; (2) the polar edges can further be spin-paired when edge-reconstruction fulfills the ECM for both the double cation (Mo, Si)-edge and the anion N-edge; and (3) ECM and CPA give the same conclusion for edge-reconstruction. Our analysis of combining ECM and CPA not only gives the general guidance for obtaining spin-paired and semiconducting polar edges but also potentially helps deepen the understanding of edges of other 2D layered materials