Atomic-Layer-Deposited Aluminum Oxide Thin Films Probed with X-ray Scattering and Compared to Molecular Dynamics and Density Functional Theory Models.

A better understanding of amorphous aluminum oxide's structure and electronic properties is obtained through combined experimental and computational approaches. Grazing incidence X-ray scattering measurements were carried out on aluminum oxide thin films grown using thermal atomic layer deposition. The corresponding pair distribution functions (PDFs) showed structures similar to previously reported PDFs of solid-state amorphous alumina and molten alumina. Structural models based on crystalline alumina polymorphs (PDFgui) and amorphous alumina (molecular dynamics, MD) were examined for structural comparisons to the experimental PDF data. Smaller MD models were optimized and verified against larger models to allow for quantum chemical electronic structure calculations. The electronic structure of the amorphous alumina models yields additional insight into the band structure and electronic defects present in amorphous alumina that are not present in crystalline samples.

Shedding X-ray Light on the Interfacial Electrochemistry of Silicon Anodes for Li-Ion Batteries.

Electrochemical alloying reactions of group IV elements, such as Si, Ge, or Sn, with lithium provide a promising route to next-generation anode materials for lithium-ion batteries (LIBs) due to their high volumetric and gravimetric capacities. However, commercialization of these anodes is still sparse owing to quick capacity fading and limited Coulombic efficiency, which arise from large volume expansion leading to particle cracking and subsequent electrochemical inactivity. As a result, the solid electrolyte interphase (SEI), originating in the decomposition of the electrolyte upon battery operation outside the electrolyte's thermodynamic stability window, grows uncontrollably. While a large number of mitigation strategies have been developed, an improved nanometer level fundamental understanding of the (de)lithiation process and SEI formation, growth, and evolution is necessary to overcome these challenges. Toward this end, many experimental and theoretical approaches have been utilized but still provide an incomplete picture. This is due to the difficulty of investigating buried interfaces and interphases of lithiation products and thin SEI layers (nanometer-scale) in situ and with the desired nanometer accuracy. In this Account, we illustrate the utilization of in situ X-ray reflectivity (XRR) to provide nanometer-scale insights on the SEI nucleation, growth, and evolution, and well as the (de)lithiation process of Si electrodes. XRR is a nondestructive and surface- and interface-sensitive technique that allows for in situ investigations during battery operation under realistic electrochemical conditions. Insight into the system is provided via the surface-normal density profile, which is interpreted in terms of thickness, density, and roughness of individual surface layers, allowing monitoring of the interfacial morphology and chemistry evolution, through which the SEI growth and Si (de)lithiation process can be resolved. We utilized a model battery anode consisting of a native oxide terminated single crystalline Si wafer in half cell configuration with standard electrolyte in a specifically designed in situ XRR electrochemical cell. We have resolved the nucleation and formation process of the inner inorganic SEI and have observed two well-defined inorganic SEI layers on Si anodes: a bottom-SEI layer (adjacent to the electrode) formed via the lithiation of the native oxide and a top-SEI layer mainly consisting of the electrolyte decomposition product, LiF. This SEI layer grows during lithiation and contracts during delithiation. Further, our results show that the lithiation of crystalline Si (c-Si) is a layer-by-layer, reaction-limited, two-phase process with a well-defined phase boundary between LixSi lithiation product and c-Si; in contrast, the delithiation of LixSi and the lithiation of amorphous Si (a-Si) are reaction-limited, single-phase processes. Moreover, we resolved the influences of current density and the Si crystallographic orientation of the reaction interface on the (de)lithiation process. The implications of our findings are discussed with regard to battery performance.

In Situ Study of Silicon Electrode Lithiation with X-ray Reflectivity.

Surface sensitive X-ray reflectivity (XRR) measurements were performed to investigate the electrochemical lithiation of a native oxide terminated single crystalline silicon (100) electrode in real time during the first galvanostatic discharge cycle. This allows us to gain nanoscale, mechanistic insight into the lithiation of Si and the formation of the solid electrolyte interphase (SEI). We describe an electrochemistry cell specifically designed for in situ XRR studies and have determined the evolution of the electron density profile of the lithiated Si layer (LixSi) and the SEI layer with subnanometer resolution. We propose a three-stage lithiation mechanism with a reaction limited, layer-by-layer lithiation of the Si at the LixSi/Si interface.

Measurement and Modeling of Short and Medium Range Order in Amorphous Ta2O5 Thin Films.

Amorphous films and coatings are rapidly growing in importance. Yet, there is a dearth of high-quality structural data on sub-micron films. Not understanding how these materials assemble at atomic scale limits fundamental insights needed to improve their performance. Here, we use grazing-incidence x-ray total scattering measurements to examine the atomic structure of the top 50-100 nm of Ta2O5 films; mirror coatings that show high promise to significantly improve the sensitivity of the next generation of gravitational-wave detectors. Our measurements show noticeable changes well into medium range, not only between crystalline and amorphous, but also between as-deposited, annealed and doped amorphous films. It is a further challenge to quickly translate the structural information into insights into mechanisms of packing and disorder. Here, we illustrate a modeling approach that allows translation of observed structural features to a physically intuitive packing of a primary structural unit based on a kinked Ta-O-Ta backbone. Our modeling illustrates how Ta-O-Ta units link to form longer 1D chains and even 2D ribbons, and how doping and annealing influences formation of 2D order. We also find that all the amorphousTa2O5 films studied in here are not just poorly crystalline but appear to lack true 3D order.

Structure of the floating water bridge and water in an electric field.

The floating water bridge phenomenon is a freestanding rope-shaped connection of pure liquid water, formed under the influence of a high potential difference (approximately 15 kV). Several recent spectroscopic, optical, and neutron scattering studies have suggested that the origin of the bridge is associated with the formation of anisotropic chains of water molecules in the liquid. In this work, high energy X-ray diffraction experiments have been performed on a series of floating water bridges as a function of applied voltage, bridge length, and position within the bridge. The two-dimensional X-ray scattering data showed no direction-dependence, indicating that the bulk water molecules do not exhibit any significant preferred orientation along the electric field. The only structural changes observed were those due to heating, and these effects were found to be the same as for bulk water. These X-ray scattering measurements are supported by molecular dynamics (MD) simulations which were performed under electric fields of 10(6) V/m and 10(9) V/m. Directional structure factor calculations were made from these simulations parallel and perpendicular to the E-field. The 10(6) V/m model showed no significant directional-dependence (anisotropy) in the structure factors. The 10(9) V/m model however, contained molecules aligned by the E-field, and had significant structural anisotropy.

Dramatically enhanced cleavage of the C-C bond using an electrocatalytically coupled reaction.

This paper describes a generalized approach for the selective electrocatalytic C-C bond splitting in aliphatic alcohols at low temperature in aqueous state, with ethanol as an example. We show that selective C-C bond cleavage, leading to carbon dioxide, is possible in high pH aqueous media at low overpotentials. This improved selectivity and activity is achieved using a solution-born co-catalyst based on Pb(IV) acetate, which controls the mode of the ethanol adsorption so as to facilitate direct activation of the C-C bond. The simultaneously formed under-potentially deposited (UPD) Pb and surface lead hydroxide change the functionality of the catalyst surface for efficient promotion of CO oxidation. The resulting catalyst retains an unprecedented ability to sustain the full oxidation reaction pathway on an extended time scale of hours as opposed to minutes without addition of Pb(IV) acetate.

Structural and mechanistic revelations on an iron conversion reaction from pair distribution function analysis.

Not simply small particles: pair distribution function analysis yields comprehensive insights into the electrochemical reaction of α-Fe(2)O(3) with lithium. The metallic Fe formed in this reaction was found to be defect-rich nanoparticles that restructure continuously without growing-an unusual characteristic likely linked to its highly reversible capacity.

Efficient simultaneous reverse Monte Carlo modeling of pair-distribution functions and extended x-ray-absorption fine structure spectra of crystalline disordered materials.

An efficient implementation of simultaneous reverse Monte Carlo (RMC) modeling of pair distribution function (PDF) and EXAFS spectra is reported. This implementation is an extension of the technique established by Krayzman et al. [J. Appl. Cryst. 42, 867 (2009)] in the sense that it enables simultaneous real-space fitting of x-ray PDF with accurate treatment of Q-dependence of the scattering cross-sections and EXAFS with multiple photoelectron scattering included. The extension also allows for atom swaps during EXAFS fits thereby enabling modeling the effects of chemical disorder, such as migrating atoms and vacancies. Significant acceleration of EXAFS computation is achieved via discretization of effective path lengths and subsequent reduction of operation counts. The validity and accuracy of the approach is illustrated on small atomic clusters and on 5500-9000 atom models of bcc-Fe and α-Fe(2)O(3). The accuracy gains of combined simultaneous EXAFS and PDF fits are pointed out against PDF-only and EXAFS-only RMC fits. Our modeling approach may be widely used in PDF and EXAFS based investigations of disordered materials.