Concept: Phase transition
Recently, superconductivity was found on semiconductor surface reconstructions induced by metal adatoms, promising a new field of research where superconductors can be studied from the atomic level.Here we measure the electron transport properties of the Si(111)-(¿7 × ¿3)-In surface near the resistive phase transition and analyze the data in terms of theories of two-dimensional (2D) superconductors.In the normal state, the sheet resistances (2D resistivities) R¿ of the samples decrease significantly between 20 and 5 K, suggesting the importance of the electron-electron scattering in electron transport phenomena.The decrease in R¿ is progressively accelerated just above the transition temperature (Tc) due to the direct (Aslamazov-Larkin term) and the indirect (Maki-Thompson term) superconducting fluctuation effects.A minute but finite resistance tail is found below Tc down to the lowest temperature of 1.8 K, which may be ascribed to a dissipation due to free vortex flow.The present study lays the ground for a future research aiming to find new superconductors in this class of materials.
We have produced a superconducting binary-elements intercalated graphite, CaxSr1-xCy, with the intercalation of Sr and Ca in highly-oriented pyrolytic graphite; the superconducting transition temperature, T c, was ~3 K. The superconducting CaxSr1-xCy sample was fabricated with the nominal x value of 0.8, i.e., Ca0.8Sr0.2Cy. Energy dispersive X-ray (EDX) spectroscopy provided the stoichiometry of Ca0.5(2)Sr0.5(2)Cy for this sample, and the X-ray powder diffraction (XRD) pattern showed that Ca0.5(2)Sr0.5(2)Cy took the SrC6-type hexagonal-structure rather than CaC6-type rhombohedral-structure. Consequently, the chemical formula of CaxSr1-xCy sample could be expressed as ‘Ca0.5(2)Sr0.5(2)C6’. The XRD pattern of Ca0.5(2)Sr0.5(2)C6 was measured at 0-31 GPa, showing that the lattice shrank monotonically with increasing pressure up to 8.6 GPa, with the structural phase transition occurring above 8.6 GPa. The pressure dependence of T c was determined from the DC magnetic susceptibility and resistance up to 15 GPa, which exhibited a positive pressure dependence of T c up to 8.3 GPa, as in YbC6, SrC6, KC8, CaC6 and Ca0.6K0.4C8. The further application of pressure caused the rapid decrease of T c. In this study, the fabrication and superconducting properties of new binary-elements intercalated graphite, CaxSr1-xCy, are fully investigated, and suitable combinations of elements are suggested for binary-elements intercalated graphite.
- Proceedings of the National Academy of Sciences of the United States of America
- Published 7 months ago
Water exists in high- and low-density amorphous ice forms (HDA and LDA), which could correspond to the glassy states of high- (HDL) and low-density liquid (LDL) in the metastable part of the phase diagram. However, the nature of both the glass transition and the high-to-low-density transition are debated and new experimental evidence is needed. Here we combine wide-angle X-ray scattering (WAXS) with X-ray photon-correlation spectroscopy (XPCS) in the small-angle X-ray scattering (SAXS) geometry to probe both the structural and dynamical properties during the high-to-low-density transition in amorphous ice at 1 bar. By analyzing the structure factor and the radial distribution function, the coexistence of two structurally distinct domains is observed at T = 125 K. XPCS probes the dynamics in momentum space, which in the SAXS geometry reflects structural relaxation on the nanometer length scale. The dynamics of HDA are characterized by a slow component with a large time constant, arising from viscoelastic relaxation and stress release from nanometer-sized heterogeneities. Above 110 K a faster, strongly temperature-dependent component appears, with momentum transfer dependence pointing toward nanoscale diffusion. This dynamical component slows down after transition into the low-density form at 130 K, but remains diffusive. The diffusive character of both the high- and low-density forms is discussed among different interpretations and the results are most consistent with the hypothesis of a liquid-liquid transition in the ultraviscous regime.
Olivine lithium iron phosphate is a technologically important electrode material for lithium-ion batteries and a model system for studying electrochemically driven phase transformations. Despite extensive studies, many aspects of the phase transformation and lithium transport in this material are still not well understood. Here we combine operando hard X-ray spectroscopic imaging and phase-field modeling to elucidate the delithiation dynamics of single-crystal lithium iron phosphate microrods with long-axis along the  direction. Lithium diffusivity is found to be two-dimensional in microsized particles containing ~3% lithium-iron anti-site defects. Our study provides direct evidence for the previously predicted surface reaction-limited phase-boundary migration mechanism and the potential operation of a hybrid mode of phase growth, in which phase-boundary movement is controlled by surface reaction or lithium diffusion in different crystallographic directions. These findings uncover the rich phase-transformation behaviors in lithium iron phosphate and intercalation compounds in general and can help guide the design of better electrodes.
The microscopic kinetics of ubiquitous solid-solid phase transitions remain poorly understood. Here, by using single-particle-resolution video microscopy of colloidal films of diameter-tunable microspheres, we show that transitions between square and triangular lattices occur via a two-step diffusive nucleation pathway involving liquid nuclei. The nucleation pathway is favoured over the direct one-step nucleation because the energy of the solid/liquid interface is lower than that between solid phases. We also observed that nucleation precursors are particle-swapping loops rather than newly generated structural defects, and that coherent and incoherent facets of the evolving nuclei exhibit different energies and growth rates that can markedly alter the nucleation kinetics. Our findings suggest that an intermediate liquid should exist in the nucleation processes of solid-solid transitions of most metals and alloys, and provide guidance for better control of the kinetics of the transition and for future refinements of solid-solid transition theory.
Large thermal changes driven by a magnetic field have been proposed for environmentally friendly energy-efficient refrigeration, but only a few materials that suffer hysteresis show these giant magnetocaloric effects. Here we create giant and reversible extrinsic magnetocaloric effects in epitaxial films of the ferromagnetic manganite La(0.7)Ca(0.3)MnO(3) using strain-mediated feedback from BaTiO(3) substrates near a first-order structural phase transition. Our findings should inspire the discovery of giant magnetocaloric effects in a wide range of magnetic materials, and the parallel development of nanostructured bulk samples for practical applications.
Grain boundaries separate crystallites in solids and influence material properties, as widely documented for bulk materials. In nanomaterials, however, investigations of grain boundaries are very challenging and just beginning. Here, we report the systematic mapping of the role of grain boundaries in the hydrogenation phase transformation in individual Pd nanoparticles. Employing multichannel single-particle plasmonic nanospectroscopy, we observe large variation in particle-specific hydride-formation pressure, which is absent in hydride decomposition. Transmission Kikuchi diffraction suggests direct correlation between length and type of grain boundaries and hydride-formation pressure. This correlation is consistent with tensile lattice strain induced by hydrogen localized near grain boundaries as the dominant factor controlling the phase transition during hydrogen absorption. In contrast, such correlation is absent for hydride decomposition, suggesting a different phase-transition pathway. In a wider context, our experimental setup represents a powerful platform to unravel microstructure-function correlations at the individual-nanoparticle level.
The sensitive response of the nematic graphene oxide (GO) phase to external stimuli makes this phase attractive for extending the applicability of GO and reduced GO to solution processes and electro-optic devices. However, contrary to expectations, the alignment of nematic GO has been difficult to control through the application of electric fields or surface treatments. Here, we show that when interflake interactions are sufficiently weak, both the degree of microscopic ordering and the direction of macroscopic alignment of GO liquid crystals (LCs) can be readily controlled by applying low electric fields. We also show that the large polarizability anisotropy of GO and Onsager excluded-volume effect cooperatively give rise to Kerr coefficients that are about three orders of magnitude larger than the maximum value obtained so far in molecular LCs. The extremely large Kerr coefficient allowed us to fabricate electro-optic devices with macroscopic electrodes, as well as well-aligned, defect-free GO over wide areas.
Ultrafast photoinduced phase transitions could revolutionize data-storage and telecommunications technologies by modulating signals in integrated nanocircuits at terahertz speeds. In quantum phase-changing materials (PCMs), microscopic charge, lattice, and orbital degrees of freedom interact cooperatively to modify macroscopic electrical and optical properties. Although these interactions are well documented for bulk single crystals and thin films, little is known about the ultrafast dynamics of nanostructured PCMs when interfaced to another class of materials as in this case to active plasmonic elements. Here, we demonstrate how a mesh of gold nanoparticles, acting as a plasmonic photocathode, induces an ultrafast phase transition in nanostructured vanadium dioxide (VO2) when illuminated by a spectrally resonant femtosecond laser pulse. Hot electrons created by optical excitation of the surface-plasmon resonance in the gold nanomesh are injected ballistically across the Au/VO2 interface to induce a subpicosecond phase transformation in VO2. Density functional calculations show that a critical density of injected electrons leads to a catastrophic collapse of the 6 THz phonon mode, which has been linked in different experiments to VO2 phase transition. The demonstration of subpicosecond phase transformations that are triggered by optically induced electron injection opens the possibility of designing hybrid nanostructures with unique nonequilibrium properties as a critical step for all-optical nanophotonic devices with optimizable switching thresholds.
To stabilize the copper and aluminum ions in simulated sludge, a series of sintering processes were conducted to transform Cu/Al precipitation into spinel structure, CuAl(2)O(4). The results indicated that the large amount of salt content in the simulated sludge would hinder the formation of crystalline CuAl(2)O(4) generated from the incorporation of CuO and Al(2)O(3), even after the sintering process at 1200°C. Opposite to the amorphous CuAl(2)O(4), the crystalline CuAl(2)O(4) can be formed in the sintering process at 700-1100°C for 3h with the desalinating procedure. According to the theory of free energy, the experimental data and references, the best formation temperature of CuAl(2)O(4) was determined at 900-1000°C. As the temperature rose to 1200°C, CuAlO(2) was formed with the dissociation of CuAl(2)O(4). The XPS analysis also showed that the binding energy of copper species in the simulated sludge was switched from 933.8eV for Cu(II) to 932.8eV for Cu(I) with the variation of temperature. In this system, the leaching concentration of copper and aluminum ions from sintered simulated sludge was decreased with ascending temperature and reached the lowest level at 1000°C. Furthermore, the descending tendency coincided with the formation tendency of spinel structure and the diminishing of copper oxide.