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1. Investigations of water/oxide interfaces by molecular dynamics simulations

   https://doi.org/10.1002/wcms.1537  

   Wang, Ruiyu ; Klein, Michael L. ; Carnevale, Vincenzo ; Borguet, Eric ( June 2021 , WIREs Computational Molecular Science)

   Water/oxide interfaces are ubiquitous on earth and show significant influence on many chemical processes. For example, understanding water and solute adsorption as well as catalytic water splitting can help build better fuel cells and solar cells to overcome our looming energy crisis; the interaction between biomolecules and water/oxide interfaces is one hypothesis to explain the origin of life. However, knowledge in this area is still limited due to the difficulty of studying water/solid interfaces. As a result, research using increasingly sophisticated experimental techniques and computational simulations has been carried out in recent years. Although it is difficult for experimental techniques to provide detailed microscopic structural information, molecular dynamics (MD) simulations have satisfactory performance. In this review, we discuss classical and ab initio MD simulations of water/oxide interfaces. Generally, we are interested in the following questions: How do solid surfaces perturb interfacial water structure? How do interfacial water molecules and adsorbed solutes affect solid surfaces and how do interfacial environments affect solvent and solute behavior? Finally, we discuss progress in the application of neural network potential based MD simulations, which offer a promising future because this approach has already enabled ab initio level accuracy for very large systems and long trajectories.

   This article is categorized under:

   Theoretical and Physical Chemistry > Spectroscopy

   Molecular and Statistical Mechanics > Molecular Interactions

   Structure and Mechanism > Molecular Structures

    

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2. Surface stability of SrNbO3+δ grown by hybrid molecular beam epitaxy

   https://doi.org/10.1063/5.0097699  

   Thapa, Suresh ; Provence, Sydney R. ; Gemperline, Patrick T. ; Matthews, Bethany E. ; Spurgeon, Steven R. ; Battles, Sydney L. ; Heald, Steve M. ; Kuroda, Marcelo A. ; Comes, Ryan B. ( September 2022 , APL Materials)

   4d transition metal oxides have emerged as promising materials for numerous applications including high mobility electronics. SrNbO3 is one such candidate material, serving as a good donor material in interfacial oxide systems and exhibiting high electron mobility in ultrathin films. However, its synthesis is challenging due to the metastable nature of the d1 Nb4+ cation and the limitations in the delivery of refractory Nb. To date, films have been grown primarily by pulsed laser deposition (PLD), but development of a means to grow and stabilize the material via molecular beam epitaxy (MBE) would enable studies of interfacial phenomena and multilayer structures that may be challenging by PLD. To that end, SrNbO3 thin films were grown using hybrid MBE for the first time using a tris(diethylamido)(tert-butylimido) niobium precursor for Nb and an elemental Sr source on GdScO3 substrates. Varying thicknesses of insulating SrHfO3 capping layers were deposited using a hafnium tert-butoxide precursor for Hf on top of SrNbO3 films to preserve the metastable surface. Grown films were transferred in vacuo for x-ray photoelectron spectroscopy to quantify elemental composition, density of states at the Fermi energy, and Nb oxidation state. Ex situ studies by x-ray absorption near edge spectroscopy and scanning transmission electron microscopy illustrate that the SrHfO3 capping plays an important role in preserving the crystalline quality of the material and the Nb 4d1 metastable charge state under atmospheric conditions.

    

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3. Oxygen Reduction Electrocatalysis with Epitaxially Grown Spinel MnFe 2 O 4 and Fe 3 O 4

   https://doi.org/10.1021/acscatal.1c05172  

   Bredar, Alexandria R. ; Blanchet, Miles D. ; Burton, Andricus R. ; Matthews, Bethany E. ; Spurgeon, Steven R. ; Comes, Ryan B. ; Farnum, Byron H. ( March 2022 , ACS Catalysis)

   Nanocrystalline MnFe2O4 has shown promise as a catalyst for the oxygen reduction reaction (ORR) in alkaline solutions, but the material has been sparingly studied as highly ordered thin-film catalysts. To examine the role of surface termination and Mn and Fe site occupancy, epitaxial MnFe2O4 and Fe3O4 spinel oxide films were grown on (001)- and (111)-oriented Nb:SrTiO3 perovskite substrates using molecular beam epitaxy and studied as electrocatalysts for the oxygen reduction reaction (ORR). High-resolution X-ray diffraction (HRXRD) and X-ray photoelectron spectroscopy (XPS) show the synthesis of pure phase materials, while scanning transmission electron microscopy (STEM) and reflection high-energy electron diffraction (RHEED) analysis demonstrate island-like growth of (111) surface-terminated pyramids on both (001)- and (111)-oriented substrates, consistent with the literature and attributed to the lattice mismatch between the spinel films and the perovskite substrate. Cyclic voltammograms under a N2 atmosphere revealed distinct redox features for Mn and Fe surface termination based on comparison of MnFe2O4 and Fe3O4. Under an O2 atmosphere, electrocatalytic reduction of oxygen was observed at both Mn and Fe redox features; however, a diffusion-limited current was only achieved at potentials consistent with Fe reduction. This result contrasts with that of nanocrystalline MnFe2O4 reported in the literature where the diffusion-limited current is achieved with Mn-based catalysis. This difference is attributed to a low density of Mn surface termination, as determined by the integration of current from CVs collected under N2, in addition to low conductivity through the MnFe2O4 film due to the degree of inversion. Such low densities are attributed to the synthetic method and island-like growth pattern and highlight challenges in studying ORR catalysis with single-crystal spinel materials. 

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4. Influence of Oxygen Vacancy and Top Electrode on Switching Behavior of InGaZnO Based Resistive Random Access Memory

   Qin, Fei ; Lee, Sunghwan ( June 2022 , 64th Electronic Materials Conference)

   Biomimetic synaptic processes, which are imitated by functional memory devices in the computer industry, are a key focus of artificial intelligence (AI) research. It is critical to developing a memory technology that is compatible with Brain-Inspired Computing in order to eliminate the von Neumann bottleneck that restricts the efficiency of traditional computer designs. Due to restrictions such as high operation voltage, poor retention capacity, and high power consumption, silicon-based flash memory, which presently dominates the data storage devices market, is having difficulty meeting the requirements of future data storage device development. The developing resistive random-access memory (RRAM) has sparked intense investigation because of its simple two-terminal structure: two electrodes and a switching layer. RRAM has a resistive switching phenomenon which is a cycling behavior between the high resistance state and the low resistance state. This developing device type is projected to outperform traditional memory devices. Indium gallium zinc oxide (IGZO) has attracted great attention for the RRAM switching layer because of its high transparency and high atomic diffusion property of oxygen atoms. More importantly, by controlling the oxygen ratio in the sputter gas, its electrical properties can be easily tuned. The IGZO has been applied to the thin-film transistor (TFT), thus, it is very promising to integrate RRAM with TFT. In this work, we proposed IGZO-based RRAMs. ITO was chosen as the bottom electrode towards achieving a fully transparent memristor. And for the IGZO switching layer, we varied the O2/Ar ratio during the deposition to modify the oxygen vacancy of IGZO. Through the XPS measurement, we confirmed that the higher O2/Ar ratio can lower the oxygen vacancy concentration. We also chose ITO as the top electrode, for the comparison, two active metals copper and silver were tested for the top electrode materials. For our IGZO layer, the best ratio of O2/Ar is the middle value. And copper top electrode device has the most stable cycling switching and the silver one is perfect for large memory window, however, it encounters a stability issue. The optical transmission examination was performed using a UV-Vis spectrometer, and the average transmittance of the complete devices in the visible-light wavelength range was greater than 90%, indicating good transparency. 50nm, 100nm, and 150nm RS layers of IGZO RRAM were produced to explore the thickness dependency on the characteristics of the RS layer. Also, because the oxygen vacancy concentration influences the RS and RRAM performance, the oxygen partial pressure during IGZO sputtering was modified to maximize the property. Electrode selection is critical and can have a significant influence on the device's overall performance. As a result, Cu TE was chosen for our second type of device because Cu ion diffusion can aid in the development of conductive filaments (CF). Finally, between the TE and RS layers, a 5 nm SiO2 barrier layer was used to limit Cu penetration into the RS layer. Simultaneously, this SiO2 inserting layer can offer extra interfacial series resistance in the device, lowering the off current and, as a result, improving the on/off ratio and overall performance. In conclusion, transparent IGZO-based RRAMs have been created. The thickness of the RS layer and the sputtering conditions of the RS layer were modified to tailor the property of the RS layer. A series of TE materials and a barrier layer were incorporated into an IGZO-based RRAM and the performance was evaluated in order to design the TE material's diffusion capabilities to the RS layer and the BE. Our positive findings show that IGZO is a potential material for RRAM applications and overcoming the existing memory technology limitation. 

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5. Solid‐state sintering of core‐shell ceramic powders fabricated by particle atomic layer deposition

   https://doi.org/10.1111/jace.17079  

   O'Toole, Rebecca J. ; Buur, Peter J. ; Gump, Christopher J. ; Musgrave, Charles B. ; Weimer, Alan W. ( March 2020 , Journal of the American Ceramic Society)

   The properties of technical ceramics are highly dependent on their microstructure, which evolves during sintering. Sintering is the process by which ceramic parts are subjected to high temperatures to activate chemical diffusion and the consumption of porosity. During the initial stage of sintering, interparticle necks between neighboring particles form and subsequently increase in size, consuming porosity as the particle centers move closer together. To experimentally determine how this process depends on particle surface composition, particle atomic layer deposition (ALD) was used to deposit a thin film of amorphous aluminum oxide (Al₂O₃) onto yttria‐stabilized tetragonal zirconia (3YSZ) particles, producing core‐shell structured powders. The uniformity of the Al₂O₃film was confirmed with transmission electron microscopy and energy dispersive spectroscopy. Scanning electron microscopy was used to observe microstructural evolution during sintering, and the dihedral angles of Al₂O₃and 3YSZ grains were measured to determine the ratio of interfacial energies between the 3YSZ|3YSZ, 3YSZ|Al₂O₃, and Al₂O₃|Al₂O₃interfaces. Analysis of the densification kinetics revealed that the initial stage of densification is dependent on the material at the surface of the particles (ie, the Al₂O₃film) and is controlled by the diffusion of Al³⁺cations through Al₂O₃. Once the Al₂O₃film has coalesced, the sintering behavior is controlled by the densification of the core material (3YSZ). Thus, core‐shell powders fabricated by particle ALD sinter by a two‐step process where the kinetics are dependent on the material present at interparticle contacts.

    

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