Lightning-induced high temperature and pressure microstructures in surface and subsurface fulgurites.

Cloud-to-ground lightning causes both high-temperature and high-pressure metamorphism of rocks, forming rock fulgurite. We demonstrate that a range of microstructural features indicative of high temperatures and pressures can form in fulgurites at the surface and in fractures up to several meters below the surface. In comparison to a granite reference sample collected from a borehole at a depth of 138 m, microstructures in both the surface and fracture fulgurite are characterized by: (i) the presence of glass, (ii) a phase transformation in K-feldspar with the presence of exsolution lamellae of plagioclase, and (iii) high residual stresses up to 1.5 GPa. Since this is the first time that fracture-related fulgurite has been described, we also carried out a 1-D numerical model to investigate the processes by which these can form. The model shows that the electric current density in fractures up to 40 m from the landing point can be as high as that on the surface, providing an explanation for the occurrence of fracture-related fulgurites. Our work broadens the near-surface environments in which rock fulgurite has been reported, and provides a detailed description of microstructures that can be compared to those formed during other types of extreme metamorphic events.

Rechargeable Na/Cl2 and Li/Cl2 batteries.

Lithium-ion batteries (LIBs) are widely used in applications ranging from electric vehicles to wearable devices. Before the invention of secondary LIBs, the primary lithium-thionyl chloride (Li-SOCl2) battery was developed in the 1970s using SOCl2 as the catholyte, lithium metal as the anode and amorphous carbon as the cathode1-7. This battery discharges by lithium oxidation and catholyte reduction to sulfur, sulfur dioxide and lithium chloride, is well known for its high energy density and is widely used in real-world applications; however, it has not been made rechargeable since its invention8-13. Here we show that with a highly microporous carbon positive electrode, a starting electrolyte composed of aluminium chloride in SOCl2 with fluoride-based additives, and either sodium or lithium as the negative electrode, we can produce a rechargeable Na/Cl2 or Li/Cl2 battery operating via redox between mainly Cl2/Cl- in the micropores of carbon and Na/Na+ or Li/Li+ redox on the sodium or lithium metal. The reversible Cl2/NaCl or Cl2/LiCl redox in the microporous carbon affords rechargeability at the positive electrode side and the thin alkali-fluoride-doped alkali-chloride solid electrolyte interface stabilizes the negative electrode, both are critical to secondary alkali-metal/Cl2 batteries.

Twinning-mediated anomalous alignment of rutile films revealed by synchrotron X-ray nanodiffraction.

Nanotwin structures in materials engender fascinating exotic properties. However, twinning usually alter the crystal orientation, resulting in random orientation and limited performances. Here, we report a well-aligned rutile TiO2 nanotwin film with superior preferential orientation than its isostructural substrate. By means of the synchrotron X-ray Laue nanodiffraction technique, the crystal orientation, twin boundaries, and deviatoric stresses of the film were quantitatively imaged at unprecedented spatial resolution to unravel the underlying mechanism of this anomalous alignment. Massive {101}-type rutile nanotwins were observed, and a crystallographic relationship of the heteroepitaxy was proposed. The rapid twinning and twin-controlled heteroepitaxy are responsible for the texture improvement. This work would open up opportunities for rational design of better twin-based functional materials, and implies the powerful capabilities of X-ray nanodiffraction technique for multidisciplinary applications.

Fabrication of Large-Scale High-Mobility Flexible Transparent Zinc Oxide Single Crystal Wafers.

Single crystal wafers, such as silicon, are the fundamental carriers of advanced electronic devices. However, these wafers exhibit rigidity without mechanical flexibility, limiting their applications in flexible electronics. Here, we propose a new approach to fabricate 1.5 in. flexible functional zinc oxide (ZnO) single crystal wafers with high electron mobility (>100 cm2 V-1 s-1) and optical transparency (>80%) by a combination of thin-film deposition, a chemical solution method, and surficial treatment. The uniformity of the flexible single crystal wafers is examined by an advanced scanning X-ray diffraction technique and photoluminescence spectroscopy. The transport properties of ZnO flexible single crystal wafers retain their pristine states under various bending conditions, including cyclability and endurability. This approach demonstrates a breakthrough in the fabrication of the flexible single crystal wafers for future flexible optoelectronic applications.

Nanoporous Silver Telluride for Active Hydrogen Evolution.

Silver-based nanomaterials have been versatile building blocks of various photoassisted energy applications; however, they have demonstrated poor electrochemical catalytic performance and stability, in particular, in acidic environments. Here we report a stable and high-performance electrochemical catalyst of silver telluride (AgTe) for the hydrogen evolution reaction (HER), which was synthesized with a nanoporous structure by an electrochemical synthesis method. X-ray spectroscopy techniques on the nanometer scale and high-resolution transmission electron microscopy revealed an orthorhombic structure of nanoporous AgTe with precise lattice constants. First-principles calculations show that the AgTe surface possesses highly active catalytic sites for the HER with an optimized Gibbs free energy change of hydrogen adsorption (-0.005 eV). Our nanoporous AgTe demonstrates exceptional stability and performance for the HER, an overpotential of 27 mV, and a Tafel slope of 33 mV/dec. As a stable catalyst for hydrogen production, AgTe is comparable to platinum-based catalysts and provides a breakthrough for high-performance electrochemical catalysts.

Nanoprobing of MoS2 by Synchrotron Radiation When van der Waals Epitaxy Is Locally Invalid.

In this work, we demonstrated nano-scaled Laue diffractions by a focused polychromatic synchrotron radiation beam to discover what happens in MoS2 when van der Waals epitaxy is locally invalid. A stronger exciton recombination with a local charge depletion in the density of 1 × 1013 cm-2, extrapolated by Raman scattering and photoluminescence, occurs in grains, which exhibits a preferred orientation of 30° rotation with respect to the c-plane of a sapphire substrate. Else, the charge doping and trion recombination dominate instead. In addition to the breakthrough in extrapolating mesoscopic crystallographic characteristics, this work opens the feasibility to manipulate charge density by the selection of the substrate-induced disturbances without external treatment and doping. Practically, the 30° rotated orientation in bilayer MoS2 films is promoted on inclined facets in the patterned sapphire substrate, which exhibits a periodic array of charge depletion of about 1.65 × 1013 cm-2. The built-in manipulation of carrier concentrations could be a potential candidate to lateral and large-area electronics based on 2D materials.

Electroreduction of CO2 to Formate on a Copper-Based Electrocatalyst at High Pressures with High Energy Conversion Efficiency.

Electrocatalytic CO2 reduction (CO2RR) to valuable fuels is a promising approach to mitigate energy and environmental problems, but controlling the reaction pathways and products remains challenging. Here a novel Cu2O nanoparticle film was synthesized by square-wave (SW) electrochemical redox cycling of high-purity Cu foils. The cathode afforded up to 98% Faradaic efficiency for electroreduction of CO2 to nearly pure formate under ≥45 atm CO2 in bicarbonate catholytes. When this cathode was paired with a newly developed NiFe hydroxide carbonate anode in KOH/borate anolyte, the resulting two-electrode high-pressure electrolysis cell achieved high energy conversion efficiencies of up to 55.8% stably for long-term formate production. While the high-pressure conditions drastically increased the solubility of CO2 to enhance CO2 reduction and suppress hydrogen evolution, the (111)-oriented Cu2O film was found to be important to afford nearly 100% CO2 reduction to formate. The results have implications for CO2 reduction to a single liquid product with high energy conversion efficiency.

Element Effects on High-Entropy Alloy Vacancy and Heterogeneous Lattice Distortion Subjected to Quasi-equilibrium Heating.

We applied Simmons-Balluffi methods, positron measurements, and neutron diffraction to estimate the vacancy of CoCrFeNi and CoCrFeMnNi high-entropy alloys (HEAs) using Cu as a benchmark. The corresponding formation enthalpies and associated entropies of the HEAs and Cu were calculated. The vacancy-dependent effective free volumes in both CoCrFeNi and CoCrFeMnNi alloys are greater than those in Cu, implying the easier formation of vacancies by lattice structure relaxation of HEAs at elevated temperatures. Spatially resolved synchrotron X-ray measurements revealed different characteristics of CoCrFeNi and CoCrFeMnNi HEAs subjected to quasi-equilibrium conditions at high temperatures. Element-dependent behavior revealed by X-ray fluorescence (XRF) mapping indicates the effect of Mn on the Cantor Alloy.

Evolution of a Novel Ribbon Phase in Optimally Doped Bi2Sr2CaCu2O8+δ at High Pressure and Its Implication to High- TC Superconductivity.

One challenge in studying high-temperature superconductivity (HTSC) stems from a lack of direct experimental evidence linking lattice inhomogeneity and superconductivity. Here, we apply synchrotron hard X-ray nanoimaging and small-angle scattering to reveal a novel micron-scaled ribbon phase in optimally doped Bi2Sr2CaCu2O8+δ (Bi-2212, with δ = 0.1). The morphology of the ribbon-like phase evolves simultaneously with the dome-shaped TC behavior under pressure. X-ray absorption studies show that the increasing of TC is associated with oxygen-hole redistribution in the CuO2 plan, while TC starts to decrease with pressure when oxygen holes become immobile. Additional X-ray irradiation experiments reveal that nanoscaled short-range ordering of oxygen vacancies could further lower TC, which indicates that the optimal TC is affected not only by an optimal morphology of the ribbon phase, but also an optimal distribution of oxygen vacancies. Our studies thereby provide for the first time compelling experimental evidence correlating the TC with micron to nanoscale inhomogeneity.

Thermal effect of Zn quantum dots grown on Si(111): competition between relaxation and reconstraint.

Zn dots are potential solutions for metal contacts in future nanodevices. The metastable states that exist at the interface between Zn quantum dots and oxide-free Si(111) surfaces can suppress the development of the complete relaxation and increase the size of Zn dots. In this work, the actual heat consumption of the structural evolution of Zn dots resulting from extrinsic thermal effect was analyzed. Zn dots were coherently grown on oxide-free Si(111) through magnetron RF sputtering. A compensative optical method combined with reflective second harmonic generation and synchrotron x-ray diffraction (XRD) was developed to statistically analyze the thermal effect on the Zn dot system. Pattern matching (3 m) between the Zn and oxide-free Si(111) surface enabled Si(111) to constrain Zn dots from a liquid to solid phase. Annealing under vacuum induced smaller, loose Zn dots to be reconstrained by Si(111). When the size of the Zn dots was in the margin of complete relaxation, the Zn dot was partially constrained by potential barriers (metastable states) between Zn(111) and one of the six in-planes of Si〈110〉. The thermal disturbance exerted by annealing would enable partially constrained ZnO/Zn dots to overcome the potential barrier and be completely relaxed, which is obvious on the transition between Zn(111) and Zn(002) peak in synchrotron XRD. Considering the actual irradiated surface area of dots array in a wide-size distribution, the competition between reconstrained and relaxed Zn dots on Si(111) during annealing was statistically analyzed.

Enhanced electrical properties and field emission characteristics of AZO/ZnO-nanowire core-shell structures.

The electrical properties and field-emission characteristics of ZnO nanowires (ZnO-NWs) fabricated using a vapor-liquid-solid method were systematically investigated. In particular, we explored the effects of Al-doped ZnO (AZO) films (thickness 4-100 nm) deposited on ZnO-NWs using an atomic layer deposition (ALD) method on the optoelectronic properties. The results show that the sheet resistance of net-like ZnO-NW structures can be significantly improved, specifically to become ∼1/1000 of the sheet resistance of the as-grown ZnO-NWs, attaining less than 10 Ω Sq(-1). The emission current density measured at the maximum field was roughly quadrupled relative to that of the as-grown ZnO-NWs. The data of the enhanced field-emission characteristics show that, with the ALD system, the AZO films of small resistance are readily coated on a structure with a high aspect ratio and the coating radius is controlled relative to the turn-on voltage and current density. The ultrathin AZO film from a one-monolayer coating process also significantly improved emission properties through modification of the effective work function at the AZO/ZnO-NW surface.

Crystal Orientation Dynamics of Collective Zn dots before Preferential Nucleation.

The island nucleation in the context of heterogeneous thin film growth is often complicated by the growth kinetics involved in the subsequent thermodynamics. We show how the evolution of sputtered Zn island nucleation on Si(111) by magnetron sputtering in a large area can be completely understood as a model system by combining reflective second harmonic generation (RSHG), a 2D pole figure with synchrotron X-ray diffraction. Zn dots are then oxidized on the surfaces when exposed to the atmosphere as Zn/ZnO dots. Derived from the RSHG patterns of Zn dots at different growth times, the Zn dots grow following a unique transition from kinetic to thermodynamic control. Under kinetic-favoring growth, tiny Zn dots prefer arranging themselves with a tilted c-axis to the Si(111) substrate toward any of the sixfold in-plane Si<110> directions. Upon growth, the Zn dots subsequently evolve themselves to a metastable state with a smaller tilting angle toward selective <110> directions. As the Zn dots grow over a critical size, they become most thermodynamically stable with the c-axis vertical to the Si(111) substrate. For a system with large lattice mismatch, small volume dots take kinetic pathways with insignificant deviations in energy barriers.

Ultrathin oriented BiFeO3 films from deposition of atomic layers with greatly improved leakage and ferroelectric properties.

Highly (001)-oriented BiFeO3 ultrathin films of total thickness of less than 10 nm were deposited on Si(001) substrates via deposition of atomic layers (ALD) with a LaNiO3 buffer. A radio-frequency (RF)-sputtered sample of the same thickness was prepared for comparison. The ALD combined with interrupted flow and an exchange reaction between Bi and Fe precursors provides a superior method to grow ternary compounds. According to X-ray diffraction, upon deposition at a temperature of less than 550 °C, the only phase in the film was BiFeO3. Anomalous fine structure from synchrotron X-ray diffraction certified the valence bonding through the BiFeO3 (001) diffraction signal. The stoichiometric ratio of BiFeO3 obtained from X-ray photoelectron spectroscopy indicated that ALD has a proportion much improved over the RF preparation, and this is also in agreement with the results for diffraction anomalous fine structure. The use of high-resolution transmission electron and atomic force microscopes showed that the layer structure and morphology from ALD presented a satisfactory coverage, more conformal than that with the RF method. The BiFeO3 thin film deposited with ALD shows excellent leakage, improved at least 1000 times with respect to the RF preparation, making this method suitable for the fabrication of ferroelectric random-access memory devices. From the hysteresis loop, the largest remanent polarization was observed as 2Pr = 2.0 µC cm(-2).

Sputter-prepared (001) BiFeO3 thin films with ferromagnetic L10-FePt(001) electrode on glass substrates.

Highly textured BiFeO3(001) films were formed on L10-FePt(001) bottom electrodes on glass substrates by sputtering at reduced temperature of 400°C. Good electric polarization 2Pr = 80 and 95 µC/cm2, comparable to that of the reported epitaxial films, and coercivity Ec = 415 and 435 kV/cm are achieved in the samples with 20-nm- and 30-nm-thick electrodes. The BiFeO3(001) films show different degrees of compressive strain. The relation between the variations of strain and 2Pr suggests that the enhancement of 2Pr resulted from the strain-induced rotation of spontaneous polarization. The presented results open possibilities for the applications based on electric-magnetic interactions.