We report on the synthesis, stability, and local structure of In2O3 thin films grown via rf-magnetron sputtering and characterized by in-situ x-ray scattering and focused x-ray nanodiffraction. We find that In2O3 deposited onto (0 0 1)-oriented single crystal yttria-stabilized zirconia substrates adopts a Stranski–Krastanov growth mode at a temperature of 850 °C, resulting in epitaxial, truncated square pyramids with (1 1 1) side walls. We find that at this temperature, the pyramids evaporate unless they are stabilized by a low flux of In2O3 from the magnetron source. We also find that the internal lattice structure of one such pyramid is made up of differently strained volumes, revealing local structural heterogeneity that may impact the properties of In2O3 nanostructures and films.

Four-terminal measurements of impedance spectra have long been troubled by the presence of high frequency artifacts that typically indicate unphysically large inductive behavior. We follow up on the observation of Fleig et al., that voltage and current are necessarily measured in different locations of the potentiostat circuit, and that, typically, the electrometer input is a virtual ground. In this case, the capacitance of coaxial cables that connect sample electrodes to the potentiostat provides a high frequency conduction path to ground, so that some of the current that passes through the sample bypasses the electrometer. In four-electrode measurements, this mechanism produces the observed inductive artifacts. We examine a variety of simulated samples, with calculations compared to measurements of relevant circuits, to quantitatively investigate the nature of the artifacts. Model results agree with measurements when the leakage capacitances are properly included in the circuit analyses. With understanding of the origin of the inductive artifacts, the four-electrode method can be effectively utilized, enabling a combination of two-, three-and four-electrode measurements to be used to best advantage. Using this combination of electrode configurations, temperature dependent measurements of SrTiO3, Y2O3-stabilized ZrO2, and In2O3 films deposited on YSZ substrates are presented. (C) The Author(s) 2014. Published by ECS. This is an open access article distributed under the terms of the Creative Commons Attribution Non-Commercial No Derivatives 4.0 License (CC BY-NC-ND, http://creativecommons.org/licenses/by-nc-nd/4.0/), which permits non-commercial reuse, distribution, and reproduction in any medium, provided the original work is not changed in any way and is properly cited. For permission for commercial reuse, please email: oa@electrochem.org. All rights reserved.

Many complex oxides display an array of structural instabilities often tied to altered electronic behavior. For oxide heterostructures, several different interfacial effects can dramatically change the nature of these instabilities. Here, we investigate LaAlO3/SrTiO3 (001) heterostructures using synchrotron x-ray scattering. We find that when cooling from high temperature, LaAlO3 transforms from the \documentclass[12pt]{minimal}\begin{document}$Pm\bar{3}m$\end{document}Pm3¯m to the Imma phase due to strain. Furthermore, the first 4 unit cells of the film adjacent to the substrate exhibit a gradient in rotation angle that can couple with polar displacements in films thinner than that necessary for 2D electron gas formation.

Polymer-assisted deposition (PAD) is one of the chemical solution deposition methods which have been successfully used to grow films, form coatings, and synthesize nanostructured materials. In comparison with other conventional solution-based deposition techniques, PAD differs in its use of water-soluble polymers in the solution that prevent the metal ions from unwanted chemical reactions and keep the solution stable. Furthermore, filtration to remove non-coordinated cations and anions in the PAD process ensures well controlled nucleation, which enables the growth of high quality epitaxial films with desired structural and physical properties. The precursor solution is prepared by mixing water-soluble polymer(s) with salt(s). Thermal treatment of the precursor films in a controlled environment leads to the formation of desired materials. Using BaTiO3 grown on SrTiO3 and LaMnO3 on LaAlO3 as model systems, we show the effect of filtration on the nucleation and growth of epitaxial complex metal-oxide films based on the PAD process.

In the growing field of in operando and in situ X-ray experiments, there exists a large disparity in the types of environments and equipment to control them. This situation makes it challenging to conduct multiple experiments with a single mechanical interface to the diffractometer. Here, we describe the design and implementation of a modular instrument mounting system that can be installed on a standard six-circle diffractometer (e.g., 5021 Huber GmbH). This new system allows for the rapid changeover of different chambers and sample heaters and permits accurate sample positioning (x, y, z, and azimuthal rotation) without rigid coupling to the chamber body. Isolation of the sample motion from the chamber enclosure is accomplished through a combination of custom rotary seals and bellows. Control of the pressure and temperature has been demonstrated in the ranges of 10(-6)-10(3) Torr and 25°C-900°C, respectively. We have utilized the system with several different modular instruments. As an example, we provide in situ sputtering results, where the growth dynamics of epitaxial LaGaO3 thin films on (001) SrTiO3 substrates were investigated.

In order to study irradiation damage and inert gas bubble formation and growth behaviors, and to provide results and insights useful towards the validation of a multi-scale simulation approach based on a newly developed Xe-Mo inter-atomic potential, in situ Transmission Electron Microscopy (TEM) studies of Xe implantations in pure single crystal Molybdenum (Mo) have been conducted. 300 key and 400 keV Xer ion beams were used to implant Xe in pre-thinned TEM Mo specimens. The irradiations were conducted at 300 degrees C and 600 degrees C to ion fluence up to 4 x 1016 ions/cm(2).In situ TEM characterization allows detailed behaviors of defect clusters to be observed and is very useful in illustrating defect interaction mechanisms and processes. Dislocation loops were found to form at relatively low irradiation fluence levels. The characterization results showed that the free surfaces, formed in the process of producing pre-thinned specimens, play an important role in influencing the behaviors of dislocation loops. Similar characterizations were conducted at high fluence levels where Xe gas bubbles can be clearly observed. Xe gas bubbles were observed to form by a multi-atom nucleation process and they were immobile throughout the irradiation process at both temperatures. Measurements on both the number density and the size of dislocation loops and gas bubbles were taken. The results and implications of the measurements are discussed in this paper. Published by Elsevier B.V.

The paper describes a novel transmission electron microscopy (TEM) experiment with in situ ion irradiation designed to improve and validate a computer model. TEM thin foils of molybdenum were irradiated in situ by 1 MeV Kr ions up to similar to 0.045 displacements per atom (dpa) at 80 degrees C at three dose rates -5 x 10(-6), 5 x 10(-5), and 5 x 10(-4) dpa/s - at the Argonne IVEMTandem Facility. The low-dose experiments produced visible defect structure in dislocation loops, allowing accurate, quantitative measurements of defect number density and size distribution. Weak beam darkfield plane-view images were used to obtain defect density and size distribution as functions of foil thickness, dose, and dose rate. Diffraction contrast electron tomography was performed to image defect clusters through the foil thickness and measure their depth distribution. A spatially dependent cluster dynamic model was developed explicitly to model the damage by 1 MeV Kr ion irradiation in an Mo thin foil with temporal and spatial dependence of defect distribution. The set of quantitative data of visible defects was used to improve and validate the computer model. It was shown that the thin foil thickness is an important variable in determining the defect distribution. This additional spatial dimension allowed direct comparison between the model and experiments of defect structures. The defect loss to the surfaces in an irradiated thin foil was modeled successfully. TEM with in situ ion irradiation of Mo thin foils was also explicitly designed to compare with neutron irradiation data of the identical material that will be used to validate the model developed for thin foils.

In situ synchrotron x-ray techniques were used to investigate oxygen surface exchange behavior in thin film La0.6Sr0.4Co0.2Fe0.8O3−δ (LSCF)/Gd2O3-doped CeO2/Y2O3-stabilized ZrO2 heterostructures. Applying electrical potentials across the heterostructures results in significant expansion or contraction of the out-of-plane LSCF lattice parameter, indicating changes in the LSCF oxygen vacancy concentration. Oxygen transport across the LSCF/atmosphere interface is found to be rate limiting under both cathodic and anodic conditions.

The sputter-induced epitaxy change of in-plane orientation occurring in YBa2Cu3O7-x (001) thin films grown on MgO (001) substrates by pulsed organo-metallic beam epitaxy (POMBE) is investigated by a series of film growth and characterization experiments, including RBS and TEM. The factors influencing the orientation change are systematically studied. The experimental results suggest that the substrate surface morphology change caused by the ion sputtering and the Ar ion implantation in the substrate surface layer are not the major factors that affect the orientation change. Instead, the implantation of W ions, which come from the hot filament of the ion gun, and the initial Ba deposition layer in the YBCO film growth play the most important roles in controlling the epitaxy orientation change. Microstructure studies show that a BaxMg1-xO buffer layer is formed on top of the sputtered substrate surface due to Ba diffusion into the W implanted layer. It is believed that the formation of this buffer layer relieves the large lattice mismatch and changes the YBCO film from the 45° oriented growth to the 0° oriented growth.

ABSTRACTInterdiffusion of Fe and B trilayer specimens during 1-MeV Kr+ bombardment was studied using Rutherford backscattering and electron microscopy. The square of the interdiffusion distance during mixing at 300°C was found to depend linearly on the irradiation dose. Arrhenius behavior with an apparent activation enthalpy of 0.7 eV was observed for the mixing between 200 and 500°C. Electron microscopy of ion-beam mixed multilayer specimens revealed that two crystalline compounds, Fe2B and Fe3B, formed during bombardment at 450°C, while two different amorphous Fe/B phases formed at 300°C. Substantially improved adhesion and reduced friction were observed for Fe/B multilayers ion-beam mixed onto M50 steel substrates at 450°C.

Nanocrystalline BaTiO3 has been synthesized for the first time by a gas-condensation process using an electron beam evaporation system. BaTiO3 and Ti sources are vaporized simultaneously in either a mixed helium-oxygen or pure helium environment. Nano-BaTiO3 particles have an average particle size of approximately 18 nm. The processing parameters of the evaporation process are reported.

The melt phase alloying of Ni-Au films on Ni substrates has been studied for rapid quenches following 35 nano-second Q switched ruby laser pulses (0.69µ wavelength) in the energy regime of 0.5 to 3.0 j/cm2. The Ni and Au films were each 200 Å in thickness having been deposited on a polished Ni substrate by standard hot ribbon vapor deposition methods. Data was obtained on pre and post alloyed surface layers using Rutherford backscattering, transmission electron microscopy, and STEM energy dispersive X-ray analysis. The melting and resolidification dynamics of the liquid-solid interface was monitored through finite difference integration of the non-linear heat conduction equation to give temperature profiles, depth of melting and melt front velocities associated with the liquid-solid phase change. Resolidification velocities were typically 15 meters/second with melt depths extending to a few thousand angstroms depending on pulse energy. RBS data confirms that liquid phase diffusion of gold in nickel has occured. TEM analysis reveals the presence of a two phase mixture being composed of nickel rich and gold rich material. Microbeam energy dispersive X-ray analysis indicates the presence of a relatively uniform mixing of these two Phases. Pronounced one dimensional solute segregation was not observed in these specimens, however, overall penetration depths of the gold was somewhat larger for the lower energy densities than for the larger ones. Also, unusual circular cell patterns were observed in the resolidified material, their contrast being enhanced by preferential etching during the TEM specimen polishing procedure.

The utility of in situ synchrotron x-ray scattering and fluorescence in gaining insight into the early stages of the atomic layer deposition process is demonstrated in this study of ZnO growth on Si. ZnO films are found to initially grow as islands, with the onset of coalescence occurring during the fourth growth cycle. The start of coalescence is accompanied by a small increase in surface roughness. After ten cycles of growth, the growth rate decreases from 4.2 to 3.0 Å per cycle, with the growth following expected self-limiting behavior. The overall growth process is consistent with the model of Puurunen and Vandervorts for substrate-inhibited growth [R. L. Puurunen and W. Vandervorst, J. Appl. Phys. 96, 7686 (2004)].

We observe that the high-temperature delta-phase of Bi2O3 is stabilized to room temperature by the epitaxial growth of nanostructures onto either (001)-oriented SrTiO3 or (001)(p)-oriented DyScO3 single crystal substrates. In addition, the morphology can be controlled by the miscut of the substrate. Synchrotron x-ray scattering observations at controlled temperatures and oxygen partial pressures reveal that the delta-Bi2O3 nanostructures are coherently strained to the substrates at room temperature. Annealing the nanostructures at 600 degrees C causes gradual conversion of the (001)-oriented delta-phase to an unidentified strain-relaxed phase.

An in situ environmental transmission electron microscopy study of the nucleation and growth of oxide islands during the early-stage oxidation of (001) Cu1-xAux alloys (x <= 38 at. %) was undertaken in order to investigate the effects of alloying on oxide island nucleation behavior and growth kinetics. The kinetic data reveal that Au enhances the nucleation density of oxide islands and suppresses their growth rate. Our results provide insight into reasons for the decreased passivation properties of Cu when alloyed with Au. (c) 2007 American Institute of Physics.

In situ transmission electron microscopy observations of the oxidation of (001) Cu-Au alloys indicate that the Cu2O islands that form undergo a remarkable transformation from an initially compact morphology to a dendritic structure as growth proceeds. Correspondingly, the surface composition becomes nonuniform and the fractal dimension associated with the islands evolves from 2.0 to a stable value of 1.87, indicating a transition in the rate-limiting mechanism of oxidation from oxygen surface diffusion to diffusion of copper through the increasingly gold-rich regions adjacent to the islands.

In situ synchrotron x-ray studies of the early-stage oxidation behavior of Cu (001) reveal that for Cu2O nanoislands, the Cu–Cu2O equilibrium phase boundary is shifted to larger oxygen partial pressure (pO2) by many orders of magnitude relative to bulk Cu2O. Real-time scattering measurements find that an ordered surface structure appears with increasing pO2, followed by the nucleation of epitaxial Cu2O nanoislands. By adjusting the pO2, it is possible to reversibly grow or shrink these islands and accurately determine the equilibrium phase boundary. These observations provide insight into the general stability of oxide nanoclusters grown by various techniques.