Surface and grain boundary coating for stabilizing LiNi0.8Mn0.1Co0.1O2 based electrodes.

The widespread use of high-capacity Ni-rich layered oxides such as LiNi0.8Mn0.1Co0.1O2 (NMC811), in lithium-ion batteries is hindered due to practical capacity loss and reduced working voltage during operation. Aging leads to defective NMC811 particles, affecting electrochemical performance. Surface modification offers a promising approach to improve cycle life. Here, we introduce an amorphous lithium titanate (LTO) coating via atomic layer deposition (ALD), not only covering NMC811 surfaces but also penetrating cavities and grain boundaries. As NMC811 electrodes suffer from low structural stability during charge and discharge, We combined electrochemistry, operando X-ray diffraction (XRD), and dilatometry to understand structural changes and the coating protective effects. XRD reveals significant structural evolution during delithiation for uncoated NMC811. The highly reversible phase change in coated NMC811 highlights enhanced bulk structure stability. The LTO coating retards NMC811 degradation, boosting capacity retention from 86% to 93% after 140 cycles. This study underscores the importance of grain boundary engineering for Ni-rich layered oxide electrode stability and the interplay of chemical and mechanical factors in battery aging.

High Voltage Cycling Stability of LiF-Coated NMC811 Electrode.

The development of LiNi0.8Mn0.1Co0.1O2 (NMC811) as a cathode material for high-energy-density lithium-ion batteries (LIBs) intends to address the driving limitations of electric vehicles. However, the commercialization of this technology has been hindered by poor cycling stability at high cutoff voltages. The potential instability and drastic capacity fade stem from irreversible parasitic side reactions at the electrode-electrolyte interface. To address these issues, a stable nanoscale lithium fluoride (LiF) coating is deposited on the NMC811 electrode via atomic layer deposition. The nanoscale LiF coating diminishes the direct contact between NMC811 and the electrolyte, suppressing the detrimental parasitic reactions. LiF-NMC811 delivers cycling stability superior to uncoated NMC811 with high cutoff voltage for half-cell (3.0-4.6 V vs Li/Li+) and full-cell (2.8-4.5 V vs graphite) configurations. The structural, morphological, and chemical analyses of the electrodes after cycling show that capacity decline fundamentally arises from the electrode-electrolyte interface growth, irreversible phase transformation, transition metal dissolution and crossover, and particle cracking. Overall, this work demonstrates that LiF is an effective electrode coating for high-voltage cycling without compromising rate performance, even at high discharge rates. The findings of this work highlight the need to stabilize the electrode-electrolyte interface to fully utilize the high-capacity performance of NMC811.

Giant anisotropic photonics in the 1D van der Waals semiconductor fibrous red phosphorus.

A confined electronic system can host a wide variety of fascinating electronic, magnetic, valleytronic and photonic phenomena due to its reduced symmetry and quantum confinement effect. For the recently emerging one-dimensional van der Waals (1D vdW) materials with electrons confined in 1D sub-units, an enormous variety of intriguing physical properties and functionalities can be expected. Here, we demonstrate the coexistence of giant linear/nonlinear optical anisotropy and high emission yield in fibrous red phosphorus (FRP), an exotic 1D vdW semiconductor with quasi-flat bands and a sizeable bandgap in the visible spectral range. The degree of photoluminescence (third-order nonlinear) anisotropy can reach 90% (86%), comparable to the best performance achieved so far. Meanwhile, the photoluminescence (third-harmonic generation) intensity in 1D vdW FRP is strong, with quantum efficiency (third-order susceptibility) four (three) times larger than that in the most well-known 2D vdW materials (e.g., MoS2). The concurrent realization of large linear/nonlinear optical anisotropy and emission intensity in 1D vdW FRP paves the way towards transforming the landscape of technological innovations in photonics and optoelectronics.

Jahn-Teller Distortion Induced Mn2+-Rich Cathode Enables Optimal Flexible Aqueous High-Voltage Zn-Mn Batteries.

Although one of the most promising aqueous batteries, all Zn-Mn systems suffer from Zn dendrites and the low-capacity Mn4+/Mn3+ process (readily leading to the occurrence of Jahn-Teller distortion, which in turn causes structural collapse and voltage/capacity fading). Here, the Mn3+ reconstruction and disproportionation are exploited to prepare the stable, Mn2+-rich manganese oxides on carbon-cloth (CMOs) in a discharged state through an inverted design, which promotes reversible Mn2+/Mn4+ kinetics and mitigates oxygen-related redox activity. Such a 1.65 V Mn2+-rich cathode enable constructing a 2.2 V Zn-Mn battery, providing a high area capacity of 4.16 mA h cm-2 (25 mA h cm-2 for 10 mL electrolyte) and superior 4000-cycle stability. Moreover, a flexible hybrid 2.7 V Zn-Mn battery is constructed using 2-pH hydrogel electrolytes to demonstrate excellent practicality and stability. A further insight has been gained to the commercial application of aqueous energy storage devices toward low-cost, high safety, and excellent energy density.

Single-step chemical vapour deposition of anti-pyramid MoS2/WS2 vertical heterostructures.

Van der Waals heterostructures are the fundamental building blocks of electronic and optoelectronic devices. Here we report that, through a single-step chemical vapour deposition (CVD) process, high-quality vertical bilayer MoS2/WS2 heterostructures with a grain size up to ∼60 µm can be synthesized from molten salt precursors, Na2MoO4 and Na2WO4. Instead of normal pyramid vertical heterostructures grown by CVD, this method synthesizes an anti-pyramid MoS2/WS2 structure, which is characterized by Raman, photoluminescence and second harmonic generation microscopy. Our facile CVD strategy for synthesizing anti-pyramid structures unveils a new synthesis route for the products of two-dimensional heterostructures and their devices for application.

Structural Phase Transitions to 2D and 3D Oxygen Vacancy Patterns in a Perovskite Film Induced by Electrical and Mechanical Nanoprobing.

Oxygen vacancy migration and ordering in perovskite oxides enable manipulation of material properties through changes in the cation oxidation state and the crystal lattice. In thin-films, oxygen vacancies conventionally order into equally spaced planes. Here, it is shown that the planar 2D symmetry is broken if a mechanical nanoprobe restricts the chemical lattice expansion that the vacancies generate. Using in situ scanning transmission electron microscopy, a transition from a perovskite structure to a 3D vacancy-ordered phase in an epitaxial La2/3 Sr1/3 MnO3- δ film during voltage pulsing under local mechanical straining is imaged. The never-before-seen ordering pattern consists of a complex network of distorted oxygen tetrahedra, pentahedra, and octahedra that, together, produce a corrugated atomic structure with lattice constants varying between 3.5 and 4.6 Å. The giant lattice distortions respond sensitively to strain variations, offering prospects for non-volatile nanoscale physical property control driven by voltage and gated by strain.

Low-loss YIG-based magnonic crystals with large tunable bandgaps.

Control of spin waves in magnonic crystals is essential for magnon-based computing. Crystals made of ferromagnetic metals offer versatility in band structure design, but strong magnetic damping restricts their transmission efficiency. Yttrium iron garnet (YIG) with ultralow damping is the palpable alternative, yet its small saturation magnetization limits dipolar coupling between discrete units. Here, we experimentally demonstrate low-loss spin-wave manipulation in magnonic crystals of physically separated nanometer-thick YIG stripes. We enhance the transmission of spin waves in allowed minibands by filling the gaps between YIG stripes with CoFeB. Thus-formed magnonic crystals exhibit tunable bandgaps of 50-200 MHz with nearly complete suppression of the spin-wave signal. We also show that Bragg scattering on only two units produces clear frequency gaps in spin-wave transmission spectra. The integration of strong ferromagnets in nanometer-thick YIG-based magnonic crystals provides effective spin-wave manipulation and low-loss propagation, a vital parameter combination for magnonic technologies.

Publisher Correction: Influence of intermixing at the Ta/CoFeB interface on spin Hall angle in Ta/CoFeB/MgO heterostructures.

A correction to this article has been published and is linked from the HTML version of this paper. The error has been fixed in the paper.

Influence of intermixing at the Ta/CoFeB interface on spin Hall angle in Ta/CoFeB/MgO heterostructures.

When a current is passed through a non-magnetic metal with strong spin-orbit coupling, an orthogonal spin current is generated. This spin current can be used to switch the magnetization of an adjacent ferromagnetic layer or drive its magnetization into continuous precession. The interface, which is not necessarily sharp, and the crystallographic structure of the nonmagnetic metal can both affect the strength of current-induced spin-orbit torques. Here, we investigate the effects of interface intermixing and film microstructure on spin-orbit torques in perpendicularly magnetized Ta/Co40Fe40B20/MgO trilayers with different Ta layer thickness (5 nm, 10 nm, 15 nm), greater than the spin diffusion length. Effective spin-orbit torques are determined from harmonic Hall voltage measurements performed at temperatures ranging from 20 K to 300 K. We account for the temperature dependence of damping-like and field-like torques by including an additional contribution from the Ta/CoFeB interface in the spin diffusion model. Using this approach, the temperature variations of the spin Hall angle in the Ta underlayer and at the Ta/CoFeB interface are determined separately. Our results indicate an almost temperature-independent spin Hall angle of [Formula: see text] in Ta and a strongly temperature-dependent [Formula: see text] for the intermixed Ta/CoFeB interface.

Direct observation of oxygen vacancy-driven structural and resistive phase transitions in La2/3Sr1/3MnO3.

Resistive switching in transition metal oxides involves intricate physical and chemical behaviours with potential for non-volatile memory and memristive devices. Although oxygen vacancy migration is known to play a crucial role in resistive switching of oxides, an in-depth understanding of oxygen vacancy-driven effects requires direct imaging of atomic-scale dynamic processes and their real-time impact on resistance changes. Here we use in situ transmission electron microscopy to demonstrate reversible switching between three resistance states in epitaxial La2/3Sr1/3MnO3 films. Simultaneous high-resolution imaging and resistance probing indicate that the switching events are caused by the formation of uniform structural phases. Reversible horizontal migration of oxygen vacancies within the manganite film, driven by combined effects of Joule heating and bias voltage, predominantly triggers the structural and resistive transitions. Our findings open prospects for ionotronic devices based on dynamic control of physical properties in complex oxide nanostructures.

Resistive Switching in All-Oxide Ferroelectric Tunnel Junctions with Ionic Interfaces.

Universal, giant and nonvolatile resistive switching is demonstrated for oxide tunnel junctions with ferroelectric PbZr0.2 Ti0.8 O3 , ferroelectric BaTiO3, and paraelectric SrTiO3 tunnel barriers. The effects are caused by reversible migration of oxygen vacancies between the tunnel barrier and bottom La2/3 Sr1/3 MnO3 electrode. The switching process, which is driven by large electric fields, is efficient down to a temperature of 5 K.

Concurrent bandgap narrowing and polarization enhancement in epitaxial ferroelectric nanofilms.

Perovskite-type ferroelectric (FE) crystals are wide bandgap materials with technologically valuable optical and photoelectric properties. Here, versatile engineering of electronic transitions is demonstrated in FE nanofilms of KTaO3, KNbO3 (KNO), and NaNbO3 (NNO) with a thickness of 10-30 unit cells. Control of the bandgap is achieved using heteroepitaxial growth of new structural phases on SrTiO3 (001) substrates. Compared to bulk crystals, anomalous bandgap narrowing is obtained in the FE state of KNO and NNO films. This effect opposes polarization-induced bandgap widening, which is typically found for FE materials. Transmission electron microscopy and spectroscopic ellipsometry measurements indicate that the formation of higher-symmetry structural phases of KNO and NNO produces the desirable red shift of the absorption spectrum towards visible light, while simultaneously stabilizing robust FE order. Tuning of optical properties in FE films is of interest for nanoscale photonic and optoelectronic devices.

Magneto-ionic control of interfacial magnetism.

In metal/oxide heterostructures, rich chemical, electronic, magnetic and mechanical properties can emerge from interfacial chemistry and structure. The possibility to dynamically control interface characteristics with an electric field paves the way towards voltage control of these properties in solid-state devices. Here, we show that electrical switching of the interfacial oxidation state allows for voltage control of magnetic properties to an extent never before achieved through conventional magneto-electric coupling mechanisms. We directly observe in situ voltage-driven O(2-) migration in a Co/metal-oxide bilayer, which we use to toggle the interfacial magnetic anisotropy energy by >0.75 erg cm(-2) at just 2 V. We exploit the thermally activated nature of ion migration to markedly increase the switching efficiency and to demonstrate reversible patterning of magnetic properties through local activation of ionic migration. These results suggest a path towards voltage-programmable materials based on solid-state switching of interface oxygen chemistry.

Electron-beam-induced Perovskite-Brownmillerite-Perovskite structural phase transitions in epitaxial La2/3Sr1/3MnO3 films.

Structural phase transitions driven by oxygen-vacancy ordering can drastically affect the properties of transition metal oxides. The focused electron beam of a transmission electron microscope (TEM) can be used to control structural phase transitions in epitaxial La2/3Sr1/3MnO3. The ability to induce and characterize oxygen-deficient structural phases simultaneously in a continuous and controllable manner opens up new pathways for atomic-scale studies of transition metal oxides and other complex materials.

Coherent piezoelectric strain transfer to thick epitaxial ferromagnetic films with large lattice mismatch.

Strain control of epitaxial films using piezoelectric substrates has recently attracted significant scientific interest. Despite its potential as a powerful test bed for strain-related physical phenomena and strain-driven electronic, magnetic, and optical technologies, detailed studies on the efficiency and uniformity of piezoelectric strain transfer are scarce. Here, we demonstrate that full and uniform piezoelectric strain transfer to epitaxial films is not limited to systems with small lattice mismatch or limited film thickness. Detailed transmission electron microscopy (TEM) and x-ray diffraction (XRD) measurements of 100 nm thick CoFe(2)O(4) and La(2/3)Sr(1/3)MnO(3) epitaxial films on piezoelectric 0.72Pb(Mg(1/3)Nb(2/3))O(3)-0.28PbTiO(3) substrates (+4.3% and -3.8% lattice mismatch) indicate that misfit dislocations near the interface do not hamper the transfer of piezoelectric strain. Instead, the epitaxial magnetic oxide films and PMN-PT substrates are strained coherently and their lattice parameters change linearly as a function of applied electric field when their remnant growth-induced strain state is negligible. As a result, ferromagnetic properties such as the coercive field, saturation magnetization, and Curie temperature can be reversibly tuned by electrical means. The observation of efficient piezoelectric strain transfer in large-mismatch heteroepitaxial structures opens up new possibilities for the engineering of strain-controlled physical properties in a broad class of hybrid material systems.

Fundamental calculations on the surface area determination of supported gold nanoparticles by alkanethiol adsorption.

Surface area determination is a crucial step for the characterization of the activity of noble metal catalysts. Not only the development of useful determination methods but foremost the understanding of surface properties and their conversion into mathematical expressions are essential to obtain reliable results. A selective method to gain access to the specific surface area of gold on oxidic supports is the chemisorption of alkanethiol from suspensions. Therefore, the concentration of a 1-dodecanthiol solution before and after immersion of supported gold catalysts was determined by gas chromatography. To convert the concentration information into a specific surface area, the surface coverage, the surface atom concentration, the interatomic Au-Au distance, and the particle morphology were considered. Further calculations afforded the determination of a mean particle diameter. A good agreement was found between gold particle sizes obtained from transmission electron microscopy and thiol adsorption. The given mathematical expressions are highly valuable for a broad range of chemisorption methods and noble metal catalysts.

Si-CdSSe core/shell nanowires with continuously tunable light emission.

Uniform Si-CdSSe core/shell nanowires were controllably synthesized by a multisource thermal evaporation route. Both the silicon core and the alloyed CdSSe shell are of high-quality and single crystalline. The silicon core is grown via the gold-catalyzed VLS route with a silicon wafer piece at the high temperature zone as the source. These preferentially grown Si nanowires further serve as templates for the afterward depositions of CdSSe shells using CdS/CdSe powders at the low temperature zone of the furnace as sources. The composition/band gap of the shells can be continuously modulated by the S/Se ratio of the evaporation sources, making these prepared heterostructures have strong and spectral position/color largely tunable light emission at the visible region. These kind of structures may have potential applications in multicolor nanoscaled light-emitting devices. This flexible growth route will also be applicable for controllable synthesis of other Si wire containing heterostructures.

Applications of mesenchymal stem cells labeled with Tat peptide conjugated quantum dots to cell tracking in mouse body.

Fluorescent quantum dots have great potential in cellular labeling and tracking. Here, PEG encapsulated CdSe/ZnS quantum dots have been conjugated with Tat peptide, and introduced into living mesenchymal stem cells. The Tat peptide conjugated quantum dots in mesenchymal stem cells were assessed by fluorescent microscopy, laser confocal microscope and. flow cytometry. The result shows that Tat peptide conjugated quantum dots could enter mesenchymal stem cells efficiently. The Tat-quantum dots labeled stem cells were further injected into the tail veins of NOD/SCID beta2 M null mice, and the tissue distribution of these labeled cells in nude mice were examined with fluorescence microscope. The result shows that characteristic fluorescence of quantum dots was observed primarily in the liver, the lung and the spleen, with little or no quantum dots accumulation in the brain, the heart, or the kidney.