Oxygen Displacement in Cuprates under Ionic Liquid Field-Effect Gating.

We studied structural changes in a 5 unit cell thick La1.96Sr0.04CuO4 film, epitaxially grown on a LaSrAlO4 substrate with a single unit cell buffer layer, when ultra-high electric fields were induced in the film by applying a gate voltage between the film (ground) and an ionic liquid in contact with it. Measuring the diffraction intensity along the substrate-defined Bragg rods and analyzing the results using a phase retrieval method we obtained the three-dimensional electron density in the film, buffer layer, and topmost atomic layers of the substrate under different applied gate voltages. The main structural observations were: (i) there were no structural changes when the voltage was negative, holes were injected into the film making it more metallic and screening the electric field; (ii) when the voltage was positive, the film was depleted of holes becoming more insulating, the electric field extended throughout the film, the partial surface monolayer became disordered, and equatorial oxygen atoms were displaced towards the surface; (iii) the changes in surface disorder and the oxygen displacements were both reversed when a negative voltage was applied; and (iv) the c-axis lattice constant of the film did not change in spite of the displacement of equatorial oxygen atoms.

Catalytic Activity and Stability of Oxides: The Role of Near-Surface Atomic Structures and Compositions.

Electrocatalysts play an important role in catalyzing the kinetics for oxygen reduction and oxygen evolution reactions for many air-based energy storage and conversion devices, such as metal-air batteries and fuel cells. Although noble metals have been extensively used as electrocatalysts, their limited natural abundance and high costs have motivated the search for more cost-effective catalysts. Oxides are suitable candidates since they are relatively inexpensive and have shown reasonably high activity for various electrochemical reactions. However, a lack of fundamental understanding of the reaction mechanisms has been a major hurdle toward improving electrocatalytic activity. Detailed studies of the oxide surface atomic structure and chemistry (e.g., cation migration) can provide much needed insights for the design of highly efficient and stable oxide electrocatalysts. In this Account, we focus on recent advances in characterizing strontium (Sr) cation segregation and enrichment near the surface of Sr-substituted perovskite oxides under different operating conditions (e.g., high temperature, applied potential), as well as their influence on the surface oxygen exchange kinetics at elevated temperatures. We contrast Sr segregation, which is associated with Sr redistribution in the crystal lattice near the surface, with Sr enrichment, which involves Sr redistribution via the formation of secondary phases. The newly developed coherent Bragg rod analysis (COBRA) and energy-modulated differential COBRA are uniquely powerful ways of providing information about surface and interfacial cation segregation at the atomic scale for these thin film electrocatalysts. In situ ambient pressure X-ray photoelectron spectroscopy (APXPS) studies under electrochemical operating conditions give additional insights into cation migration. Direct COBRA and APXPS evidence for surface Sr segregation was found for La1-xSrxCoO3-δ and (La1-ySry)2CoO4±Î´/La1-xSrxCoO3-δ oxide thin films, and the physical origin of segregation is discussed in comparison with (La1-ySry)2CoO4±Î´/La1-xSrxCo0.2Fe0.8O3-δ. Sr enrichment in many electrocatalysts, such as La1-xSrxMO3-δ (M = Cr, Co, Mn, or Co and Fe) and Sm1-xSrxCoO3, has been probed using alternative techniques, including low energy ion scattering, secondary ion mass spectrometry, and X-ray fluorescence-based methods for depth-dependent, element-specific analysis. We highlight a strong connection between cation segregation and electrocatalytic properties, because cation segregation enhances oxygen transport and surface oxygen exchange kinetics. On the other hand, the formation of cation-enriched secondary phases can lead to the blocking of active sites, inhibiting oxygen exchange. With help from density functional theory, the links between cation migration, catalyst stability, and catalytic activity are provided, and the oxygen p-band center relative to the Fermi level can be identified as an activity descriptor. Based on these findings, we discuss strategies to increase a catalyst's activity while maintaining stability to design efficient, cost-effective electrocatalysts.

Atomic structure and composition distribution in wetting layers and islands of germanium grown on silicon (001) substrates.

We present a comprehensive structural investigation of the Ge wetting layer (WL) and island growth on Si(001) substrates by a combination of AFM, high resolution transmission electron microscopy and the energy-differential coherent Bragg rod analysis (COBRA) x-ray method. By considering the influence of the initial Si surface morphology on the deposited Ge, these techniques provide quantitative information on the Ge content and its distribution, in particular within the WL which plays a crucial role in the formation of epitaxial nanostructures. In the WL, the Ge content was found to be above 80% for our growth conditions. Furthermore, from the digital analysis of high-resolution transmission electron microscope images, quantitative information on the strain relaxation is obtained, which complements the COBRA analysis of the Ge distribution and content in these nanostructures.

Anomalous Interface and Surface Strontium Segregation in (La1-ySry)2CoO4±Î´/La1-xSrxCoO3-δ Heterostructured Thin Films.

Heterostructured oxides have shown unusual electrochemical properties including enhanced catalytic activity, ion transport, and stability. In particular, it has been shown recently that the activity of oxygen electrocatalysis on the Ruddlesden-Popper/perovskite (La1-ySry)2CoO4±Î´/La1-xSrxCoO3-δ heterostructure is remarkably enhanced relative to the Ruddlesden-Popper and perovskite constituents. Here we report the first atomic-scale structure and composition of (La1-ySry)2CoO4±Î´/La1-xSrxCoO3-δ grown on SrTiO3. We observe anomalous strontium segregation from the perovskite to the interface and the Ruddlesden-Popper phase using direct X-ray methods as well as with ab initio calculations. Such Sr segregation occurred during the film growth, and no significant changes were found upon subsequent annealing in O2. Our findings provide insights into the design of highly active catalysts for oxygen electrocatalysis.

Surface x-ray diffraction results on the III-V droplet heteroepitaxy growth process for quantum dots: recent understanding and open questions.

In recent years, epitaxial growth of self-assembled quantum dots has offered a way to incorporate new properties into existing solid state devices. Although the droplet heteroepitaxy method is relatively complex, it is quite relaxed with respect to the material combinations that can be used. This offers great flexibility in the systems that can be achieved. In this paper we review the structure and composition of a number of quantum dot systems grown by the droplet heteroepitaxy method, emphasizing the insights that these experiments provide with respect to the growth process. Detailed structural and composition information has been obtained using surface X-ray diffraction analyzed by the COBRA phase retrieval method. A number of interesting phenomena have been observed: penetration of the dots into the substrate ("nano-drilling") is often encountered; interdiffusion and intermixing already start when the group III droplets are deposited, and structure and composition may be very different from the one initially intended.

Spatial dependence and mitigation of radiation damage by a line-focus mini-beam.

Recently, strategies to reduce primary radiation damage have been proposed which depend on focusing X-rays to dimensions smaller than the penetration depth of excited photoelectrons. For a line focus as used here the penetration depth is the maximum distance from the irradiated region along the X-ray polarization direction that the photoelectrons penetrate. Reported here are measurements of the penetration depth and distribution of photoelectron damage excited by 18.6 keV photons in a lysozyme crystal. The experimental results showed that the penetration depth of ~17.35 keV photoelectrons is 1.5 ± 0.2 µm, which is well below previous theoretical estimates of 2.8 µm. Such a small penetration depth raises challenging technical issues in mitigating damage by line-focus mini-beams. The optimum requirements to reduce damage in large crystals by a factor of 2.0-2.5 are Gaussian line-focus mini-beams with a root-mean-square width of 0.2 µm and a distance between lines of 2.0 µm. The use of higher energy X-rays (> 26 keV) would help to alleviate some of these requirements by more than doubling the penetration depth. It was found that the X-ray dose has a significant contribution from the crystal's solvent, which initially contained 9.0%(w/v) NaCl. The 15.8 keV photoelectrons of the Cl atoms and their accompanying 2.8 keV local dose from the decay of the resulting excited atoms more than doubles the dose deposited in the X-ray-irradiated region because of the much greater cross-section and higher energy of the excited atom, degrading the mitigation of radiation damage from 2.5 to 2.0. Eliminating heavier atoms from the solvent and data collection far from heavy-atom absorption edges will significantly improve the mitigation of damage by line-focus mini-beams.

Anomalous expansion of the copper-apical-oxygen distance in superconducting cuprate bilayers.

We have introduced an improved x-ray phase-retrieval method with unprecedented speed of convergence and precision, and used it to determine with sub-Angstrom resolution the complete atomic structure of epitaxial La(2-x)Sr(x)CuO(4) ultrathin films. We focus on superconducting heterostructures built from constituent materials that are not superconducting in bulk samples. Single-phase metallic or superconducting films are also studied for comparison. The results show that this phase-retrieval diffraction method enables accurate measurement of structural modifications in near-surface layers, which may be critically important for elucidation of surface-sensitive experiments. Specifically we find that, while the copper-apical-oxygen distance remains approximately constant in single-phase films, it shows a dramatic increase from the metallic-insulating interface of the bilayer towards the surface by as much as 0.45 A. The apical-oxygen displacement is known to have a profound effect on the superconducting transition temperature.

Atomic-scale mapping of quantum dots formed by droplet epitaxy.

Quantum dots (QDs) have applications in optoelectronic devices, quantum information processing and energy harvesting. Although the droplet epitaxy fabrication method allows for a wide range of material combinations to be used, little is known about the growth mechanisms involved. Here we apply direct X-ray methods to derive sub-ångström resolution maps of QDs crystallized from indium droplets exposed to antimony, as well as their interface with a GaAs (100) substrate. We find that the QDs form coherently and extend a few unit cells below the substrate surface. This facilitates a droplet-substrate exchange of atoms, resulting in core-shell structures that contain a surprisingly small amount of In. The work provides the first atomic-scale mapping of the interface between epitaxial QDs and a substrate, and establishes the usefulness of X-ray phasing techniques for this and similar systems.

Reducing radiation damage in macromolecular crystals at synchrotron sources.

A new strategy is presented to reduce primary X-ray damage in macromolecular crystallography. The strategy is based on separating the diffracting and damaged regions as much as feasible. The source of the radiation damage to macromolecular crystals is from two primary mechanisms: the direct excitations of electrons by absorption, and inelastic scattering of the X-rays. The first produces photoelectrons with their accompanying Auger electrons from relaxation of the core hole and the second creates Compton electrons. The properties of these two mechanisms and calculations of primary X-ray damage quantify how to modify the spatial distribution of X-rays to reduce the deleterious effects of radiation damage. By focusing the incident X-rays into vertical stripes, it is estimated that the survival (the time during which quality diffraction data can be obtained with a given X-ray flux) of large crystals can be increased by at least a factor of 1.6, while for very small platelet crystals the survival can be increased by up to a factor of 14.

Direct determination of epitaxial interface structure in Gd2O3 passivation of GaAs.

Obtaining accurate structural information on epitaxial films and interfaces is nowhere more critical than in semiconductor passivation layers, where details of the atomic structure and bonding determine the nature of the interface electronic states. Various non-destructive methods have been used to investigate the structure of films and interfaces, but their interpretation is model-dependent, leading occasionally to wrong conclusions. We have developed a new X-ray method for the direct determination of epitaxial structures, coherent Bragg rod analysis (COBRA). The usefulness of our technique is demonstrated by mapping, with atomic precision, the structure of the interfacial region of a Gd2O3 film grown epitaxially on a (100) GaAs substrate. Our findings reveal interesting behaviour not previously suggested by existing structural methods, in particular a lock-in of the in-plane Gd atomic positions to those of the Ga/As atoms of the substrate. Moreover, we find that the bulk stacking of the Gd2O3 atomic layers is abandoned in favour of a new structure that is directly correlated with the stacking sequence of the substrate. These results have important implications for Gd2O3 as an effective passivation layer for GaAs (ref. 7). Our work shows that the COBRA technique, taking advantage of the brilliance of insertion device synchrotron X-ray sources, is widely applicable to epitaxial films and interfaces.