skip to main content


Title: Molecular dynamics study of a new metastable allotropic crystalline form of gallium—supertetrahedral gallium

A new metastable crystalline form of gallium has been computationally designed using density functional calculations with imposing periodic boundary conditions. The geometric and electronic structures of the predicted new allotrope were calculated on the basis of a diamond lattice in which all carbon atoms are replaced by gallium Ga4tetrahedra. This form does not have any imaginary phonons, thus it is a metastable crystalline form of gallium. The new form of gallium is a metal and shows high plasticity and low‐melting temperature. Molecular dynamics simulations show that this form of gallium will melt at about 273 K with a sharp increase in temperature in the system during the melting process from 273 to 1800 K. This melting process is very different from conventional melting, where temperature stays the same until complete melting. That unusual melting can be explained by the fact that supertetrahedral gallium is a metastable structure that has an excess of strain energy released during melting. If made this new material may find many useful applications as a new low density metal with stored internal energy. © 2019 Wiley Periodicals, Inc.

 
more » « less
Award ID(s):
1664379
NSF-PAR ID:
10461659
Author(s) / Creator(s):
 ;  ;  ;  ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Journal of Computational Chemistry
Volume:
40
Issue:
20
ISSN:
0192-8651
Page Range / eLocation ID:
p. 1861-1865
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract

    The enhanced safety, superior energy, and power density of rechargeable metal‐air batteries make them ideal energy storage systems for application in energy grids and electric vehicles. However, the absence of a cost‐effective and stable bifunctional catalyst that can replace expensive platinum (Pt)‐based catalyst to promote oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) at the air cathode hinders their broader adaptation. Here, it is demonstrated that Tin (Sn) doped β‐gallium oxide (β‐Ga2O3) in the bulk form can efficiently catalyze ORR and OER and, hence, be applied as the cathode in Zn‐air batteries. The Sn‐doped β‐Ga2O3sample with 15% Sn (Snx=0.15‐Ga2O3) displayed exceptional catalytic activity for a bulk, non‐noble metal‐based catalyst. When used as a cathode, the excellent electrocatalytic bifunctional activity of Snx=0.15‐Ga2O3leads to a prototype Zn‐air battery with a high‐power density of 138 mW cm−2and improved cycling stability compared to devices with benchmark Pt‐based cathode. The combined experimental and theoretical exploration revealed that the Lewis acid sites in β‐Ga2O3aid in regulating the electron density distribution on the Sn‐doped sites, optimize the adsorption energies of reaction intermediates, and facilitate the formation of critical reaction intermediate (O*), leading to enhanced electrocatalytic activity.

     
    more » « less
  2. Abstract

    This work discusses the attributes, fabrication methods, and applications of gallium‐based liquid metal particles. Gallium‐based liquid metals combine metallic and fluidic properties at room temperature. Unlike mercury, which is toxic and has a finite vapor pressure, gallium possesses low toxicity and effectively zero vapor pressure at room temperature, which makes it amenable to many applications. A variety of fabrication methods produce liquid metal particles with variable sizes, ranging from nm to mm (which is the upper limit set by the capillary length). The liquid nature of gallium enables fabrication methods—such as microfluidics and sonication—that are not possible with solid materials. Gallium‐based liquid metal particles possess several notable attributes, including a metal–metal oxide (liquid–solid) core–shell structure as well as the ability to self‐heal, merge, and change shape. They also have unusual phase behavior that depends on the size of the particles. The particles have no known commercial applications, but they show promise for drug delivery, soft electronics, microfluidics, catalysis, batteries, energy harvesting, and composites. Existing challenges and future opportunities are discussed herein.

     
    more » « less
  3. The traditional von Neumann architecture limits the increase in computing efficiency and results in massive power consumption in modern computers due to the separation of storage and processing units. The novel neuromorphic computation system, an in-memory computing architecture with low power consumption, is aimed to break the bottleneck and meet the needs of the next generation of artificial intelligence (AI) systems. Thus, it is urgent to find a memory technology to implement the neuromorphic computing nanosystem. Nowadays, the silicon-based flash memory dominates non-volatile memory market, however, it is facing challenging issues to achieve the requirements of future data storage device development due to the drawbacks, such as scaling issue, relatively slow operation speed, and high voltage for program/erase operations. The emerging resistive random-access memory (RRAM) has prompted extensive research as its simple two-terminal structure, including top electrode (TE) layer, bottom electrode (BE) layer, and an intermediate resistive switching (RS) layer. It can utilize a temporary and reversible dielectric breakdown to cause the RS phenomenon between the high resistance state (HRS) and the low resistance state (LRS). RRAM is expected to outperform conventional memory device with the advantages, notably its low-voltage operation, short programming time, great cyclic stability, and good scalability. Among the materials for RS layer, indium gallium zinc oxide (IGZO) has shown attractive prospects in abundance and high atomic diffusion property of oxygen atoms, transparency. Additionally, its electrical properties can be easily modulated by controlling the stoichiometric ratio of indium and gallium as well as oxygen potential in the sputter gas. Moreover, since the IGZO can be applied to both the thin-film transistor (TFT) channel and RS layer, it has a great potential for fully integrated transparent electronics application. In this work, we proposed amorphous transparent IGZO-based RRAMs and investigated switching behaviors of the memory cells prepared with different top electrodes. First, ITO was choosing to serve as both TE and BE to achieve high transmittance. A multi-target magnetron sputtering system was employed to deposit all three layers (TE, RS, BE layers) on glass substrate. I-V characteristics were evaluated by a semiconductor parameter analyzer, and the bipolar RS feature of our RRAM devices was demonstrated by typical butterfly curves. The optical transmission analysis was carried out via a UV-Vis spectrometer and the average transmittance was around 80% out of entire devices in the visible-light wavelength range, implying high transparency. We adjusted the oxygen partial pressure during the sputtering of IGZO to optimize the property because the oxygen vacancy concentration governs the RS performance. Electrode selection is crucial and can impact the performance of the whole device. Thus, Cu TE was chosen for our second type of device because the diffusion of Cu ions can be beneficial for the formation of the conductive filament (CF). A ~5 nm SiO 2 barrier layer was employed between TE and RS layers to confine the diffusion of Cu into the RS layer. At the same time, this SiO 2 inserting layer can provide an additional interfacial series resistance in the device to lower the off current, consequently, improve the on/off ratio and whole performance. Finally, an oxygen affinity metal Ti was selected as the TE for our third type of device because the concentration of the oxygen atoms can be shifted towards the Ti electrode, which provides an oxygengettering activity near the Ti metal. This process may in turn lead to the formation of a sub-stoichiometric region in the neighboring oxide that is believed to be the origin of better performance. In conclusion, the transparent amorphous IGZO-based RRAMs were established. To tune the property of RS layer, the sputtering conditions of RS were varied. To investigate the influence of TE selections on switching performance of RRAMs, we integrated a set of TE materials, and a barrier layer on IGZO-based RRAM and compared the switch characteristics. Our encouraging results clearly demonstrate that IGZO is a promising material in RRAM applications and breaking the bottleneck of current memory technologies. 
    more » « less
  4. We report the use of suboxide molecular-beam epitaxy ( S-MBE) to grow β-Ga 2 O 3 at a growth rate of ∼1 µm/h with control of the silicon doping concentration from 5 × 10 16 to 10 19  cm −3 . In S-MBE, pre-oxidized gallium in the form of a molecular beam that is 99.98% Ga 2 O, i.e., gallium suboxide, is supplied. Directly supplying Ga 2 O to the growth surface bypasses the rate-limiting first step of the two-step reaction mechanism involved in the growth of β-Ga 2 O 3 by conventional MBE. As a result, a growth rate of ∼1 µm/h is readily achieved at a relatively low growth temperature ( T sub ≈ 525 °C), resulting in films with high structural perfection and smooth surfaces (rms roughness of <2 nm on ∼1 µm thick films). Silicon-containing oxide sources (SiO and SiO 2 ) producing an SiO suboxide molecular beam are used to dope the β-Ga 2 O 3 layers. Temperature-dependent Hall effect measurements on a 1 µm thick film with a mobile carrier concentration of 2.7 × 10 17  cm −3 reveal a room-temperature mobility of 124 cm 2  V −1  s −1 that increases to 627 cm 2  V −1  s −1 at 76 K; the silicon dopants are found to exhibit an activation energy of 27 meV. We also demonstrate working metal–semiconductor field-effect transistors made from these silicon-doped β-Ga 2 O 3 films grown by S-MBE at growth rates of ∼1 µm/h. 
    more » « less
  5. Abstract

    When in a pristine state, gallium and its alloys have the largest interfacial tensions of any liquid at room temperature. Nonetheless, applying as little as 0.8 V of electric potential across eutectic gallium indium (EGaIn) placed within aqueous sodium hydroxide (NaOH, or other electrolyte) solution will cause the metal to behave as if its interfacial tension is near zero. The mechanism behind this phenomenon has remained poorly understood because NaOH dissolves the oxide species, making it difficult to directly measure the concentration, thickness, or chemical composition of the film that forms at the interface. In addition, the oxide layers formed are atomically‐thin. Here, it presents a suite of techniques that allow to simultaneously measure both electrical and interfacial properties as a function of applied electric potential, allowing for new insights into the mechanisms, which cause the dramatic decrease in interfacial tension. A key discovery from this work is that the interfacial tension displays hysteresis while lowering the applied potential. It combines these observations with electrochemical impedance spectroscopy to evaluate how these changes in interfacial tension arise from chemical, electrical, and mechanical changes on the interface, and close with ideas for how to build a free energy model to predict these changes from first principles.

     
    more » « less