Supercritical Gallium Trichloride in Oxidative Metal Recycling: Ga2Cl6 Dimers vs GaCl3 Monomers and Rheological Behavior.

Oxidative recycling of metals is crucial for a circular economy, encompassing the preservation of natural resources, the reduction of energy consumption, and the mitigation of environmental impacts and greenhouse gas emissions associated with traditional mining and processing. Low-melting gallium trichloride appears to be a promising oxidative solvent for rare-earth metals, transuranium elements, platinum, pnictogens, and chalcogens. Typically, oxidative dissolution with GaCl3 occurs at relatively low temperatures over a few days, assuming the presence of tetrahedral Ga-Cl entities. While supercritical gallium trichloride holds the potential for advanced recycling, little is known about its structure and viscosity. Using high-energy X-ray diffraction and multiscale modeling, which includes first-principles simulations, we have revealed a dual molecular nature of supercritical gallium trichloride, consisting of tetrahedral dimers and flat trigonal monomers. The molecular geometry can be precisely tuned by adjusting the temperature and pressure, optimizing the recycling process for specific metals. The derived viscosity, consistent with the reported results in the vicinity of melting, decreases by a factor of 100 above the critical temperature, enabling fast molecular diffusion, and efficient recycling kinetics.

Gallium Trichloride Fluid: Dimer Dissociation Mechanism, Local Structure, and Atomic Dynamics.

Molten gallium trichloride emerges as a promising solvent for oxidative metal recycling. The use of supercritical fluid enhances the performance and kinetics of metal dissolution due to significantly lower viscosity in the reaction media. Additionally, the dual molecular nature of gallium trichloride, existing as edge-sharing ES-Ga2Cl6 dimers at low temperatures and high pressure, or flat trigonal GaCl3 monomers in the vicinity of the critical point and low pressures, creates the possibility to tailor the chemical geometry to a particular metallic species. Nevertheless, the mechanism of dimer dissociation, local structure, and atomic dynamics in supercritical gallium trichloride fluids are not known. Using first-principles molecular dynamics, validated by comparison with our high-energy X-ray diffraction results, we illustrate the elementary steps in dimer dissociation. These include the formation of intermediate corner-sharing CS-Ga2Cl6 dimers, the partial disproportionation of GaCl3 monomers at high temperatures and low pressures, changes in the local environment of molecular entities, and unusual atomic dynamics in supercritical fluids.

Glassy GaS: transparent and unusually rigid thin films for visible to mid-IR memory applications.

Phase-change materials based on tellurides are widely used for optical storage (DVD and Blu-ray disks), non-volatile random access memories and for development of neuromorphic computing. Narrow-gap tellurides are intrinsically limited in the telecom spectral window, where materials having a wider gap are needed. Here we show that gallium sulfide GaS thin films prepared by pulsed laser deposition reveal good transparency from the visible to the mid-IR spectral range with optical gap Eg = 2.34 eV, high refractive index nR = 2.50 over the 0.8 ≤ λ ≤ 2.5 µm range and, unlike canonical chalcogenide glasses, the absence of photo-structural transformations with a laser-induced peak power density damage threshold above 1.4 TW cm-2 at 780 nm. The origin of the excellent damage threshold under a high-power laser and UV light irradiation resides in the rigid tetrahedral structure of vitreous GaS studied by high-energy X-ray diffraction and Raman spectroscopy and supported by first-principles simulations. The average local coordination number appears to be m = 3.44, well above the optimal connectivity, 2.4 ≤ m ≤ 2.7, and the total volume of microscopic voids and cavities is 34.4%, that is, lower than for the vast majority of binary sulfide glasses. The glass-crystal phase transition in gallium sulfide thin films may be accompanied by a drastic change in the nonlinear optical properties, opening up a new dimension for memory applications in the visible to mid-IR spectral ranges.

Decoding the Atomic Structure of Ga2Te5 Pulsed Laser Deposition Films for Memory Applications Using Diffraction and First-Principles Simulations.

Neuromorphic computing, reconfigurable optical metamaterials that are operational over a wide spectral range, holographic and nonvolatile displays of extremely high resolution, integrated smart photonics, and many other applications need next-generation phase-change materials (PCMs) with better energy efficiency and wider temperature and spectral ranges to increase reliability compared to current flagship PCMs, such as Ge2Sb2Te5 or doped Sb2Te. Gallium tellurides are favorable compounds to achieve the necessary requirements because of their higher melting and crystallization temperatures, combined with low switching power and fast switching rate. Ga2Te3 and non-stoichiometric alloys appear to be atypical PCMs; they are characterized by regular tetrahedral structures and the absence of metavalent bonding. The sp3 gallium hybridization in cubic and amorphous Ga2Te3 is also different from conventional p-bonding in flagship PCMs, raising questions about its phase-change mechanism. Furthermore, gallium tellurides exhibit a number of unexpected and highly unusual phenomena, such as nanotectonic compression and viscosity anomalies just above their melting points. Using high-energy X-ray diffraction, supported by first-principles simulations, we will elucidate the atomic structure of amorphous Ga2Te5 PLD films, compare it with the crystal structure of tetragonal gallium pentatelluride, and investigate the electrical, optical, and thermal properties of these two materials to assess their potential for memory applications, among others.

GeTe2 Phase Change Material for Terahertz Devices with Reconfigurable Functionalities Using Optical Activation.

The phenomenon of phase change transition has been a fascinating research subject over decades due to a possibility of dynamically controlled materials properties, allowing the creation of optical devices with unique features. The present paper unravels the optical characteristics and terahertz (THz) dielectric permittivity of a novel phase change material (PCM), GeTe2, prepared by pulsed laser deposition (PLD) and their remarkable contrast in crystalline and amorphous states, in particular, a difference of 7 orders of magnitude in conductivity. The THz spectra were analyzed using the harmonic oscillator and Drude term. Using GeTe2 PLD films, we designed and prepared a THz metasurface in the form of periodic structure and revealed a possibility of tuning the THz resonance either by a thermal control or light-induced crystallization response, thus achieving the dynamic and tunable functionality of the metastructure. We propose controlling the state of metasurface by observing the intensity characteristics of the Raman peak of 155 cm-1. Density functional theory (DFT) modeling demonstrates that in the process of crystallization the mode intensity of 155 cm-1 assigned to Te-Te stretching in amorphous chain fragments decreases and disappears at full crystallization.

Universal Approach to Integrating Reduced Graphene Oxide into Polymer Electronics.

Flexible electronics have sparked significant interest in the development of electrically conductive polymer-based composite materials. While efforts are being made to fabricate these composites through laser integration techniques, a versatile methodology applicable to a broad range of thermoplastic polymers remains elusive. Moreover, the underlying mechanisms driving the formation of such composites are not thoroughly understood. Addressing this knowledge gap, our research focuses on the core processes determining the integration of reduced graphene oxide (rGO) with polymers to engineer coatings that are not only flexible and robust but also exhibit electrical conductivity. Notably, we have identified a particular range of laser power densities (between 0.8 and 1.83 kW/cm2), which enables obtaining graphene polymer composite coatings for a large set of thermoplastic polymers. These laser parameters are primarily defined by the thermal properties of the polymers as confirmed by thermal analysis as well as numerical simulations. Scanning electron microscopy with elemental analysis and X-ray photoelectron spectroscopy showed that conductivity can be achieved by two mechanisms-rGO integration and polymer carbonization. Additionally, high-speed videos allowed us to capture the graphene oxide (GO) modification and melt pool formation during laser processing. The cross-sectional analysis of the laser-processed samples showed that the convective flows are present in the polymer substrate explaining the observed behavior. Moreover, the practical application of our research is exemplified through the successful assembly of a conductive wristband for wearable devices. Our study not only fills a critical knowledge gap but also offers a tangible illustration of the potential impact of laser-induced rGO-polymer integration in materials science and engineering applications.

Unraveling the Atomic Structure of Bulk Binary Ga-Te Glasses with Surprising Nanotectonic Features for Phase-Change Memory Applications.

Binary Ge-Te and ternary Ge-Sb-Te systems belong to flagship phase-change materials (PCMs) and are used in nonvolatile memory applications and neuromorphic computing. The working temperatures of these PCMs are limited by low-T glass transition and crystallization phenomena. Promising high-T PCMs may include gallium tellurides; however, the atomic structure and transformation processes for amorphous Ga-Te binaries are simply missing. Using high-energy X-ray diffraction and Raman spectroscopy supported by first-principles simulations, we elucidate the short- and intermediate-range order in bulk glassy GaxTe1-x, 0.17 ≤ x ≤ 0.25, following their thermal, electric, and optical properties, revealing a semiconductor-metal transition above melting. We also show that a phase change in binary Ga-Te is characterized by a very unusual nanotectonic compression with the high internal transition pressure reaching 4-8 GPa, which appears to be beneficial for PCM applications increasing optical and electrical contrast between the SET and RESET states and decreasing power consumption.