The direct electrodeposition of crystalline germanium (Ge) nanowire film electrodes from an aqueous solution of dissolved GeO(2) using discrete 'flux' nanoparticles capable of dissolving Ge(s) has been demonstrated. Electrodeposition of Ge at inert electrode substrates decorated with small (<100 nm), discrete indium (In) nanoparticles resulted in crystalline Ge nanowire films with definable nanowire diameters and densities without the need for a physical or chemical template. The Ge nanowires exhibited strong polycrystalline character as-deposited, with approximate crystallite dimensions of 20 nm and a mixed orientation of the crystallites along the length of the nanowire. Energy dispersive spectroscopic elemental mapping of individual Ge nanowires showed that the In nanoparticles remained at the base of each nanowire, indicating good electrical communication between the Ge nanowire and the underlying conductive support. As-deposited Ge nanowire films prepared on Cu supports were used without further processing as Li(+) battery anodes. Cycling studies performed at 1 C (1624 mA g(-1)) indicated the native Ge nanowire films supported stable discharge capacities at the level of 973 mA h g(-1), higher than analogous Ge nanowire film electrodes prepared through an energy-intensive vapor-liquid-solid nanowire growth process. The cumulative data show that ec-LLS is a viable method for directly preparing a functional, high-activity nanomaterials-based device component. The work presented here is a step toward the realization of simple processes that make fully functional energy conversion/storage technologies based on crystalline inorganic semiconductors entirely through benchtop, aqueous chemistry and electrochemistry without time- or energy-intensive process steps.
Direct epitaxial growth of single-crystalline germanium (Ge) nanowires at room temperature has been performed through an electrodeposition process on conductive wafers immersed in an aqueous bath. The crystal growth is based on an electrochemical liquid-liquid-solid (ec-LLS) process involving the electroreduction of dissolved GeO2(aq) in water at isolated liquid gallium (Ga) nanodroplet electrodes resting on single-crystalline Ge or Si supports. Ge nanowires were electrodeposited on the wafer scale (>10 cm(2)) using only common glassware and a digital potentiostat. High-resolution electron micrographs and electron diffraction patterns collected from cross sections of individual substrate-nanowire contacts in addition to scanning electron micrographs of the orientation of nanowires across entire films on substrates with different crystalline orientations, supported the notion of epitaxial nanowire growth. Energy dispersive spectroscopic elemental mapping of single nanowires indicated the Ga(l) nanodroplet remains affixed to the tip of the growing nanowire throughout the nanowire electrodeposition process. Current-voltage responses measured across many individual nanowires yielded reproducible resistance values. The presented data cumulatively show epitaxial growth of covalent group IV nanowires is possible from the reduction of a dissolved oxide under purely benchtop conditions.
An electrochemical liquid-liquid-solid (ec-LLS) process that yields crystalline silicon at low temperature (80 °C) without any physical or chemical templating agent has been demonstrated. Electroreduction of dissolved SiCl(4) in propylene carbonate using a liquid gallium [Ga(l)] pool as the working electrode consistently yielded crystalline Si. X-ray diffraction and electron diffraction data separately indicated that the as-deposited materials were crystalline with the expected patterns for a diamond cubic crystal structure. Scanning and transmission electron microscopies further revealed the as-deposited materials (i.e., with no annealing) to be faceted nanocrystals with diameters in excess of 500 nm. Energy-dispersive X-ray spectra further showed no evidence of any other species within the electrodeposited crystalline Si. Raman spectra separately showed that the electrodeposited films on the Ga(l) electrodes were not composed of amorphous carbon from solvent decomposition. The cumulative data support two primary contentions. First, a liquid-metal electrode can serve simultaneously as both a source of electrons for the heterogeneous reduction of dissolved Si precursor in the electrolyte (i.e., a conventional electrode) and a separate phase (i.e., a solvent) that promotes Si crystal growth. Second, ec-LLS is a process that can be exploited for direct production of crystalline Si at much lower temperatures than ever reported previously. The further prospect of ec-LLS as an electrochemical and non-energy-intensive route for preparing crystalline Si is discussed.
As water availability becomes a growing challenge in various regions throughout the world, desalination and wastewater reclamation through technologies such as reverse osmosis (RO) are becoming more important. Nevertheless, many open questions remain regarding the internal structure of thin-film composite RO membranes. In this work, fully aromatic polyamide films that serve as the active layer of state-of-the-art water filtration membranes were investigated using high-angle annular dark-field scanning transmission electron microscopy tomography. Reconstructions of the 3D morphology reveal intricate aspects of the complex microstructure not visible from 2D projections. We find that internal voids of the active layer of compressed commercial membranes account for less than 0.2% of the total polymer volume, contrary to previously reported values that are two orders of magnitude higher. Measurements of the local variation in polyamide density from electron tomography reveal that the polymer density is highest at the permeable surface for the two membranes tested and establish the significance of surface area on RO membrane transport properties. The same type of analyses could provide explanations for different flux variations with surface area for other types of membranes where the density is distributed differently. Thus, 3D reconstructions and quantitative analyses will be crucial to characterize the complex morphology of polymeric membranes used in next-generation water-purification membranes.
Crystalline GaAs (c-GaAs) has been prepared directly through electroreduction of As(2)O(3) dissolved in an alkaline aqueous solution at a liquid gallium (Ga(l)) electrode at modest temperatures (T ≥ 80 °C). Ga(l) pool electrodes yielded consistent electrochemical behavior, affording repetitive measurements that illustrated the interdependences of applied potential, concentration of dissolved As(2)O(3), and electrodeposition temperature on the quality of the resultant c-GaAs(s). Raman spectra indicated the composition of the resultant film was strongly dependent on both the electrodeposition temperature and dissolved concentration of As(2)O(3) but not to the applied bias. For electrodepositions performed either at room temperature or with high (≥0.01 M) concentrations of dissolved As(2)O(3), Raman spectra of the electrodeposited films were consistent with amorphous As(s). X-ray diffractograms of As(s) films collected after thermal annealing indicated metallurgical alloying occurred only at temperatures in excess of 200 °C. Optical images and Raman spectra separately showed the composition of the as-electrodeposited film in dilute (≤0.001 M) solutions of dissolved As(2)O(3)(aq) was pure c-GaAs(s) at much lower temperatures than 200 °C. Diffractograms and transmission electron microscopy performed on as-prepared films confirmed the identity of c-GaAs(s). The collective results thus provide the first clear demonstration of an electrochemical liquid-liquid-solid (ec-LLS) process involving a liquid metal that serves simultaneously as an electrode, a solvent/medium for crystal growth, and a coreactant for the synthesis of a polycrystalline semiconductor. The presented data serve as impetus for the further development of the ec-LLS process as a controllable, simple, and direct route for technologically important optoelectronic materials such as c-GaAs(s).
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.