Room-Temperature Liquid Metals for Flexible Electronic Devices.

Room-temperature gallium-based liquid metals (RT-GaLMs) have garnered significant interest recently owing to their extraordinary combination of fluidity, conductivity, stretchability, self-healing performance, and biocompatibility. They are ideal materials for the manufacture of flexible electronics. By changing the composition and oxidation of RT-GaLMs, physicochemical characteristics of the liquid metal can be adjusted, especially the regulation of rheological, wetting, and adhesion properties. This review highlights the advancements in the liquid metals used in flexible electronics. Meanwhile related characteristics of RT-GaLMs and underlying principles governing their processing and applications for flexible electronics are elucidated. Finally, the diverse applications of RT-GaLMs in self-healing circuits, flexible sensors, energy harvesting devices, and epidermal electronics, are explored. Additionally, the challenges hindering the progress of RT-GaLMs are discussed, while proposing future research directions and potential applications in this emerging field. By presenting a concise and critical analysis, this paper contributes to the advancement of RT-GaLMs as an advanced material applicable for the new generation of flexible electronics.

Engineering of Cerium Modified TiNb2O7 Nanoparticles For Low-Temperature Lithium-Ion Battery.

Although TiNb2O7 (TNO) with comparable operating potential and ideal theoretical capacity is considered to be the most ideal replacement for negative Li4Ti5O12 (LTO), the low ionic and electronic conductivity still limit its practical application as satisfactory anode for lithium-ion batteries (LIBs) with high-power density. Herein, TNO nanoparticles modified by Cerium (Ce) with outstanding electrochemical performance are synthesized. The successful introduction of Ce3+ in the lattice leads to increased interplanar spacing, refined grain size, more oxygen vacancy, and a smaller lithium diffusion barrier, which are conducive to improve conductivity of both Li+ and electrons. As a result, the modified TNO reaches high reversible capacity of 256.0 mA h g-1 at 100 mA g-1 after 100 cycles, and 183.0 mA h g-1 even under 3200 mA g-1. In particular, when the temperature drops to -20 °C, the cell undergoing 1500 cycles at a high current density of 500 mA g-1 can still reach 89.7 mA h g-1, corresponding to a capacity decay rate per cycle of only 0.033%. This work provides a new way to improve the electrochemical properties of alternative anodes for LIBs at extreme temperature.

Orbital Origin of the Intrinsic Planar Hall Effect.

Recent experiments reported an antisymmetric planar Hall effect, where the Hall current is odd in the in plane magnetic field and scales linearly with both electric and magnetic fields applied. Existing theories rely exclusively on a spin origin, which requires spin-orbit coupling to take effect. Here, we develop a general theory for the intrinsic planar Hall effect (IPHE), highlighting a previously unknown orbital mechanism and connecting it to a band geometric quantity-the anomalous orbital polarizability (AOP). Importantly, the orbital mechanism does not request spin-orbit coupling, so sizable IPHE can occur and is dominated by an orbital contribution in systems with weak spin-orbit coupling. Combined with first-principles calculations, we demonstrate our theory with quantitative evaluation for bulk materials TaSb_{2}, NbAs_{2}, and SrAs_{3}. We further show that AOP and its associated orbital IPHE can be greatly enhanced at topological band crossings, offering a new way to probe topological materials.

Electric-field-tuned topological phase transition in ultrathin Na3Bi.

The electric-field-induced quantum phase transition from topological to conventional insulator has been proposed as the basis of a topological field effect transistor1-4. In this scheme, 'on' is the ballistic flow of charge and spin along dissipationless edges of a two-dimensional quantum spin Hall insulator5-9, and 'off' is produced by applying an electric field that converts the exotic insulator to a conventional insulator with no conductive channels. Such a topological transistor is promising for low-energy logic circuits4, which would necessitate electric-field-switched materials with conventional and topological bandgaps much greater than the thermal energy at room temperature, substantially greater than proposed so far6-8. Topological Dirac semimetals are promising systems in which to look for topological field-effect switching, as they lie at the boundary between conventional and topological phases3,10-16. Here we use scanning tunnelling microscopy and spectroscopy and angle-resolved photoelectron spectroscopy to show that mono- and bilayer films of the topological Dirac semimetal3,17 Na3Bi are two-dimensional topological insulators with bulk bandgaps greater than 300 millielectronvolts owing to quantum confinement in the absence of electric field. On application of electric field by doping with potassium or by close approach of the scanning tunnelling microscope tip, the Stark effect completely closes the bandgap and re-opens it as a conventional gap of 90 millielectronvolts. The large bandgaps in both the conventional and quantum spin Hall phases, much greater than the thermal energy at room temperature (25 millielectronvolts), suggest that ultrathin Na3Bi is suitable for room-temperature topological transistor operation.

Phonon Chirality Manipulation Mechanism in Transition-Metal Dichalcogenide Interlayer-Sliding Ferroelectrics.

As an ideal platform, both the theoretical prediction and first experimental verification of chiral phonons are based on transition-metal dichalcogenide materials. The manipulation of phonon chirality in these materials will have a profound effect on the study of chiral phonons. In this work, we utilize the sliding ferroelectric effect to realize the phonon chirality manipulation mechanism in transition-metal dichalcogenide materials. Based on first-principles calculations, we find the different manipulation effects of interlayer sliding on the phonon chirality and Berry curvature in bilayer and four-layer MoS2 sliding ferroelectrics. These further affect the phonon angular momentum and magnetization under a temperature gradient and the phonon Hall effect under a magnetic field. Our work connects two emerging fields and opens up a new route to manipulating phonon chirality in transition-metal dichalcogenide materials through the sliding ferroelectric mechanism.

Magnetic Real Chern Insulator in 2D Metal-Organic Frameworks.

Real Chern insulators have attracted great interest, but so far, their material realization is limited to nonmagnetic crystals and systems without spin-orbit coupling. Here, we reveal the magnetic real Chern insulator (MRCI) state in a recently synthesized metal-organic framework material Co3(HITP)2. Its ground state with in-plane ferromagnetic ordering hosts a nontrivial real Chern number, enabled by the C2zT symmetry and robustness against spin-orbit coupling. Distinct from previous nonmagnetic examples, the topological corner zero modes of MRCIs are spin-polarized. Furthermore, under small tensile strains, the material undergoes a topological phase transition from the MRCI to a magnetic double-Weyl semimetal phase, via a pseudospin-1 critical state. Similar physics can also be found in closely related materials Mn3(HITP)2 and Fe3(HITP)2, which also exist. Possible experimental detections and implications of an emerging magnetic flat band in the system are discussed.

Time-Reversal-Even Nonlinear Current Induced Spin Polarization.

We propose a time-reversal-even spin generation in second order of electric fields, which dominates the current induced spin polarization in a wide class of centrosymmetric nonmagnetic materials, and leads to a novel nonlinear spin-orbit torque in magnets. We reveal a quantum origin of this effect from the momentum space dipole of the anomalous spin polarizability. First-principles calculations predict sizable spin generations in several nonmagnetic hcp metals, in monolayer TiTe_{2}, and in ferromagnetic monolayer MnSe_{2}, which can be detected in experiment. Our work opens up the broad vista of nonlinear spintronics in both nonmagnetic and magnetic systems.

Rare-Earth Metal Complexes Supported by 1,3-Functionalized Indolyl-Based Ligands for Efficient Hydrosilylation of Alkenes.

Two different 1,3-functionalized indolyl-based proligands 1-(2-C4H7O)CH2-3-(2-tBuC6H5N═CH)C8H5N (HL1) and 1-Me2NCH2CH2-3-(2-iPrC6H5N═CH)C8H5N (HL2) were designed, prepared in high yields, and successfully applied to rare-earth metal chemistry showing different reactivities and different bondings with the central metals. The reactions of HL1 with RE(CH2SiMe3)3(THF)2 provided two types of rare-earth metal complexes: the pincer type mononuclear complexes κ3-(L1)RE(CH2SiMe3)2 [L1 = 1-(2-C4H7O)CH2-3-(2-tBuC6H5N═CH)C8H4N, RE = Lu(1), Yb(2)], and the dinuclear rare-earth metal alkyl (per alkyl/per metal) complexes having the ligand in novel coordination modes {(η1:(µ-η2:η1):η1-1-(2-C4H7O)CH2-3-[2-tBuC6H5NCH-(CH2SiMe3)]C8H4N)RECH2SiMe3}2 [RE = Er(3), Y(4), Dy(5), and Gd(6)]. Meanwhile, the reactions of HL2 with RE(CH2SiMe3)3(THF)2 led to the isolation and characterization of only the mononuclear rare-earth metal dialkyl complexes κ3-(L2)RE(CH2SiMe3)2 [L2 = 1-Me2NCH2CH2-3-(2-iPrC6H5N═CH)C8H4N, RE = Lu(7), Gd(8)] bearing the ligand in the pincer chelate form. The mononuclear complexes were formed through the sp2 C-H activation of the 2-indolyl moiety, while the dinuclear complexes were produced unexpectedly through the tandem 2-indolyl sp2 C-H activation and C═N insertion into the RE-CH2SiMe3 bond. These complexes were fully characterized by spectroscopic methods, elemental analyses, and single-crystal X-ray crystallography. The applications of the synthesized complexes as catalysts for the hydrosilylation of terminal alkenes with phenylsilane are described. Anti-Markovnikov addition products were produced by the hydrosilylation of aliphatic olefins, and Markovnikov addition products were isolated with aromatic olefins with high selectivity in the absence of cocatalysts. It is found that the dinuclear rare-earth alkyl complexes exhibited the best catalytic activity with the advantages of mild reaction conditions, short reaction time, low catalyst loading, and wide substrate applicability in comparison with the synthesized mononuclear complexes and the reported catalysts.

Chiral Phonon Diode Effect in Chiral Crystals.

The diode effect means that carriers can only flow in one direction but not the other. While diode effects for electron charge, spin, or photon have been widely discussed, it remains a question whether a chiral phonon diode can be realized, which utilizes the chiral degree of freedom of lattice vibrations. In this work, we reveal an intrinsic connection between the chiralities of a crystal structure and its phonon excitations, which naturally leads to the chiral phonon diode effect in chiral crystals. At a certain frequency, phonons with a definite chirality can propagate only in one direction but not the opposite. We demonstrate the idea in concrete materials including bulk Te and α-quartz (SiO2). Our work discovers the fundamental physics of chirality coupling between different levels of a system, and the predicted effect will provide a new route to control phonon transport and design information devices.

Intrinsic Nonlinear Electric Spin Generation in Centrosymmetric Magnets.

We propose an intrinsic nonlinear electric spin generation effect, which can dominate in centrosymmetric magnets. We reveal the band geometric origin of this effect and clarify its symmetry characters. As an intrinsic effect, it is determined solely by the material's band structure and represents a material characteristic. Combining our theory with first-principle calculations, we predict sizable nonlinear spin generation in single-layer MnBi_{2}Te_{4}, which can be detected in experiment. Our theory opens a new route for all-electric controlled spintronics in centrosymmetric magnets which reside outside of the current paradigm based on linear spin response.

MoSSe/Hf(Zr)S2 heterostructures used for efficient Z-scheme photocatalytic water-splitting.

Direct Z-scheme water-splitting is a promising route to enhancing the photocatalytic performance due to the effective separation of photogenerated carriers while simultaneously preserving the strong oxidation activity of holes and reduction activity of electrons. In this work, the MoSSe/XY2 (X = Hf, Zr; S, Se) heterostructures (HSs) with different contacts are proposed for Z-scheme photocatalytic water-spitting by first principles calculation. The separation of photogenerated carriers for HfSe2/SMoSe and ZrSe2/SMoSe HSs is limited by the type-I band alignment, while the hydrogen production ability of HfSe2/SeMoS and ZrSe2/SeMoS HSs is limited by the lower conduction band edge positions relative to the water reduction potential. The HfS2/SMoSe, HfS2/SeMoS, ZrS2/SMoSe, and ZrS2/SeMoS HSs are direct Z-scheme water-splitting photocatalysts with the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) occurring at the Hf(Zr)S2 layer and MoSSe layer, respectively. More excitingly, the S (or Se) vacancies effectively lower the HER overpotentials. Besides, the solar-to-hydrogen efficiencies are 6.1%, 5.9%, 6.4%, and 6.3% for HfS2/SMoSe, HfS2/SeMoS, ZrS2/SMoSe, and ZrS2/SeMoS HSs, respectively. This work paves the way for designing highly efficient overall water-splitting photocatalysts using 2D materials.

Propagating Chiral Phonons in Three-Dimensional Materials.

Chiral phonons were initially proposed and experimentally verified in two-dimensional (2D) systems. Their intriguing effects have generated profound impacts on multiple research fields. However, all chiral phonons reported to date are constrained to be local, in the sense that their group velocities vanish identically. Here, we propose the concept of propagating 3D chiral phonons, which can transport the information on chirality and angular momentum. Guided by the necessary conditions and using first-principles calculations, we demonstrate their existence in WN2. The chirality, group velocity, and pseudoangular momentum are analyzed. Based on their selective coupling with valley electrons and photons, we propose an experimental setup to detect the unique feature of propagating chiral phonons. Our work endows chiral phonons with a crucial character-the ability to propagate and transport quantized information, which creates a new research direction and opens up the possibility to design novel phononic quantum devices.

Half-Auxeticity and Anisotropic Transport in Pd Decorated Two-Dimensional Boron Sheets.

Upon strain, most materials shrink normal to the direction of applied strain. Similarly, if a material is compressed, it will expand in the direction orthogonal to the pressure. Few materials, those of negative Poisson ratio, show the opposite behavior. Here, we show an unprecedented feature, a material that expands normal to the direction of stress, regardless if it is strained or compressed. Such behavior, namely, half-auxeticity, is demonstrated for a borophene sheet stabilized by decorating Pd atoms. We explore Pd-decorated borophene, identify three stable phases of which one has this peculiar property of half auxeticity. After carefully analyzing stability and mechanical and electronic properties we explore the origin of this very uncommon behavior and identify it as a structural feature that may also be employed to design further 2D nanomaterials.

Intrinsic Second-Order Anomalous Hall Effect and Its Application in Compensated Antiferromagnets.

Response properties that are purely intrinsic to physical systems are of paramount importance in physics research, as they probe fundamental properties of band structures and allow quantitative calculation and comparison with experiment. For anomalous Hall transport in magnets, an intrinsic effect can appear at the second order to the applied electric field. We show that this intrinsic second-order anomalous Hall effect is associated with an intrinsic band geometric property-the dipole moment of Berry-connection polarizability (BCP) in momentum space. The effect has scaling relation and symmetry constraints that are distinct from the previously studied extrinsic contributions. Particularly, in antiferromagnets with PT symmetry, the intrinsic effect dominates. Combined with first-principles calculations, we demonstrate the first quantitative evaluation of the effect in the antiferromagnet Mn_{2}Au. We show that the BCP dipole and the resulting intrinsic second-order conductivity are pronounced around band near degeneracies. Importantly, the intrinsic response exhibits sensitive dependence on the Néel vector orientation with a 2π periodicity, which offers a new route for electric detection of the magnetic order in PT-invariant antiferromagnets.

A two-dimensional h-BN/C2N heterostructure as a promising metal-free photocatalyst for overall water-splitting.

The construction of a heterostructure (HS) is an effective strategy to modulate the desired properties of two-dimensional (2D) materials and to extend their applications. In this paper, based on the density functional theory, we predict a metal-free type-II HS formed by h-BN and C2N single layers. The h-BN/C2N HS possesses a smaller bandgap than individual h-BN and C2N single layers, and it exhibits excellent visible light absorption. Importantly, its band edge positions satisfy the requirements for spontaneous water-splitting. With the assistance of the built-in electric field across the HS and the band offset, the photoinduced carriers can be readily spatially separated. Free energy calculations indicate the high catalytic activity for water oxidation and reduction reactions. The performance can be further enhanced by strain, which modulates the bandgap and the band edge positions of the HS. The band alignment may undergo a transition from type-I to type-II under strain, offering an effective switch for the reaction. The appropriate bandgap, suitable band edge positions, and effective carrier separation make the h-BN/C2N HS a promising candidate for use as a photocatalyst in water-splitting.

Abnormal separation of the silicon-oxygen bond in the liquid layering transition of silicon dioxide in a nanoslit.

We investigated the unusual layering transition (LT) in quasi-2D liquid silicon dioxide (SiO2) confined in a nanoslit. Our results indicate that the slit size and pressure induce the abnormal LT in liquid SiO2, accompanied by a rapid change in the density, diffusion coefficient, pair correlation function and average potential energy. The silicon and oxygen atoms are almost completely separated under the extremely strong confinement effect, which is the characteristic feature of the LT. The negative slope of the LT lines in the phase diagram at different pressures suggests that a confinement-induced LT occurs at high pressure and a pressure-induced LT occurs at low pressure.

Pressure-Stabilized Semiconducting Electrides in Alkaline-Earth-Metal Subnitrides.

High pressure is able to modify profoundly the chemical bonding and generate new phase structures of materials with chemical and physical properties not accessible at ambient conditions. We here report an unprecedented phenomenon on the pressure-induced formation of semiconducting electrides via compression of layered alkaline-earth subnitrides Ca2N, Sr2N, and Ba2N that are conducting electrides with loosely confined electrons in the interlayer voids at ambient pressure. Our extensive first-principles swarm structure searches identified the high-pressure semiconducting electride phases of a tetragonal I4̅2d structure for Ca2N and a monoclinic Cc structure shared by Sr2N and Ba2N, both of which contain atomic-size cavities with paring electrons distributed within. These electride structures are validated by the excellent agreement between the simulated X-ray diffraction patterns and the experimental data available. We attribute the emergence of the semiconducting electride phases to the p-d hybridization on alkaline-earth-metal atoms under compression as well as the filling of the p-d hybridized band due to the interaction between Ca and N. Our work provides a unique example of pressure-induced metal-to-semiconductor transition in compound materials and reveals unambiguously the electron-confinement topology change between different types of electrides.

Tailoring lanthanide doping in perovskite CaTiO3 for luminescence applications.

Perovskite oxide materials have been attracting significant attention due to their rich physical and chemical properties. With its proven stability and bio-compatibility, we suggest the lanthanide-doped perovskite to be a promising material for biological luminescence applications. Here, taking CaTiO3 as a concrete example, we systematically investigate its doping properties using first-principles computational methods. We determine the conditions allowing the growth of CaTiO3 against various competing phases. We obtain the formation energies of various intrinsic point defects in the material. The doping configuration and the charge state of the lanthanide dopants are determined. We find that for heavier elements in the lanthanide family, the substitution at the Ca site is favored under p-type growth conditions and tends to be trivalent, whereas the substitution at the Ti site is favored under n-type growth conditions and tends to be divalent. And for lighter elements in the family, the substitution at the Ca site is more favored for most cases and the dopant is more likely to be trivalent. By tuning the growth conditions, one could control the valence state of the lanthanide dopant, which in turn controls the luminescence spectra. We collect and identify the emission peaks in the infrared biological window, based on which possible doping schemes are suggested for bio-labeling and imaging applications.

Liquid-Liquid Phase Transition in Nanoconfined Silicon Carbide.

We report theoretical evidence of a liquid-liquid phase transition (LLPT) in liquid silicon carbide under nanoslit confinement. The LLPT is characterized by layering transitions induced by confinement and pressure, accompanying the rapid change in density. During the layering transition, the proportional distribution of tetracoordinated and pentacoordinated structures exhibits remarkable change. The tricoordinated structures lead to the microphase separation between silicon (with the dominant tricoordinated, tetracoordinated, and pentacoordinated structures) and carbon (with the dominant tricoordinated structures) in the layer close to the walls. A strong layer separation between silicon atoms and carbon atoms is induced by strong wall-liquid forces. Importantly, the pressure confinement phase diagram with negative slopes for LLPT lines indicates that, under high pressure, the LLPT is mainly confinement-induced, but under low pressure, it becomes dominantly pressure-induced.

Sodium ferulate and n-butylidenephthalate combined with bone marrow stromal cells (BMSCs) improve the therapeutic effects of angiogenesis and neurogenesis after rat focal cerebral ischemia.

BACKGROUND: Studies have indicated that bone marrow stromal cell (BMSC) administration is a promising approach for stroke treatment. For our study, we chose sodium ferulate (SF) and n-butylidenephthalide (BP) combined with BMSC, and observed if the combination treatment possessed more significant effects on angiogenesis and neurogenesis post-stroke. METHODS: We established rat permanent middle cerebral artery occlusion (MCAo) model and evaluated ischemic volumes of MCAo, BMSC, SF + BP, Simvastatin + BMSC and SF + BP + BMSC groups with TTC staining on the 7th day after ischemia. Immunofluorescence staining of vascular endothelial growth factor (VEGF) and brain derived neurotrophic factor (BDNF), as well as immunohistochemistry staining of von Willebrand factor (vWF) and neuronal class III ß-tubulin (Tuj1) were performed in ischemic boundary zone (IBZ), furthermore, to understand the mechanism, western blot was used to investigate AKT/mammalian target of rapamycin (mTOR) signal pathway in ischemic cortex. We also tested BMSC derived-VEGF and BDNF expressions by western blot assay in vitro. RESULTS: SF + BP + BMSC group obviously decreased infarction zone, and elevated the expression of VEGF and the density and perimeter of vWF-vessels as same as Simvastatin + BMSC administration; moreover, its effects on BDNF and Tuj1 expressions were superior to Simvastatin + BMSC treatment in IBZ. Meanwhile, it showed that SF and BP combined with BMSC treatment notably up-regulated AKT/mTOR signal pathway compared with SF + BP group and BMSC alone post-stroke. Western blot results showed that SF and BP treatment could promote BMSCs to synthesize VEGF and BDNF in vitro. CONCLUSIONS: We firstly demonstrate that SF and BP combined with BMSC can significantly improve angiogenesis and neurogenesis in IBZ following stroke. The therapeutic effects are associated with the enhancement of VEGF and BDNF expressions via activation of AKT/mTOR signal pathway. Furthermore, triggering BMSC paracrine function of SF and BP might contribute to amplifying the synergic effects of the combination treatment.